Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof

ABSTRACT

Provided are a compound of Formula 7 improving the luminous efficiency, stability and life span of an organic electronic element employing the compound, the organic electronic element, and an electronic device thereof.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part of U.S. patent application Ser. No. 17/066,386, filed Oct. 8, 2020, which claims the benefit of Korean Patent Application No. KR 10-2019-0148780, filed Nov. 19, 2019, and of Korean Patent Application No. KR 10-2020-0106335, filed Aug. 24, 2020, each of which is incorporated by reference herein in its entirety.

BACKGROUND Technical Field

The present invention relates to a compound for organic electronic element, an organic electronic element using the same, and an electronic device thereof.

Background Art

In general, organic light emitting phenomenon refers to a phenomenon that converts electric energy into light energy by using an organic material. An organic electronic element using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer interposed therebetween. Here, in order to increase the efficiency and stability of the organic electronic element, the organic material layer is often composed of a multi-layered structure composed of different materials, and for example, may include a hole injection layer, a hole transport layer, an emitting layer, an electron transport layer, an electron injection layer and the like.

A material used as an organic material layer in an organic electronic element may be classified into a light emitting material and a charge transport material, such as a hole injection material, a hole transport material, an electron transport material, an electron injection material and the like depending on its function.

In the organic light emitting diode, the most problematic is the lifetime and the efficiency. As the display becomes large, the efficiency and the lifetime problem must be solved. Efficiency, life span, driving voltage and the like are related to each other. As the efficiency is increased, the driving voltage is relatively decreased, and as the driving voltage drops, the crystallization of the organic material due to joule heating generated during driving is reduced, and as a result, the life span tends to increase.

However, simply improving the organic material layer cannot maximize the efficiency. This is because, when the optimal combination of the energy level and T1 value between each organic material layer and the intrinsic properties (mobility, interface characteristics, etc.) of the material are achieved, long life and high efficiency can be achieved at the same time.

Further, recently, in organic electroluminescent devices, in order to solve the emission problem in the a hole transport layer, an emitting-auxiliary layer must be present between the hole transport layer and an emitting layer, and it is necessary to develop different emitting-auxiliary layers according to the respective emitting layers (R, G, B).

In general, electrons are transferred from the electron transport layer to the emitting layer, and holes are transferred from the hole transport layer to the emitting layer to generate excitons by recombination.

However, the material used for the hole transport layer has a low HOMO value and therefore has mostly low T1 value. As a result, the exciton generated in the emitting layer is transferred to the hole transport layer, resulting in charge unbalance in the emitting layer, and light is emitted at the interface of the hole transport layer.

When light is emitted at the interface of the hole transport layer, the color purity and efficiency of the organic electronic device are lowered and the life span is shortened. Therefore, it is urgently required to develop an emitting-auxiliary layer having a high T1 value and a HOMO level between the HOMO energy level of the hole transport layer and the HOMO energy level of the emitting layer.

Meanwhile, it is necessary to develop a hole injection layer material having stable characteristics, that is, a high glass transition temperature, against joule heating generated when the device is driven, while delaying penetration of the metal oxide from the anode electrode (ITO), which is one of the causes of shortening the lifetime of the organic electronic device, into the organic layer. The low glass transition temperature of the hole transport layer material has a characteristic that when the device is driven, the uniformity of the surface of the thin film is lowered, which has been reported to have a great influence on the lifetime of the device. In addition, OLED devices are mainly formed by a deposition method, and it is necessary to develop a material that can withstand long time in deposition, that is, a material having high heat resistance characteristics.

That is, in order to sufficiently exhibit the excellent characteristics of the organic electronic element, a material for forming an organic material layer in an element such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, an emitting-auxiliary layer material should be supported by stable and efficient materials. However, such a stable and efficient organic material layer material for an organic electronic element has not been sufficiently developed yet. Therefore, development of new materials is continuously required, and development of materials for the hole transport layer or the emitting-auxiliary layer is urgently required.

PRIOR TECHNICAL LITERATURE

Patent Literature: (Patent Document 0001) KR 1020130076842 A

BRIEF SUMMARY OF THE INVENTION

In order to solve the problems of the background art described above, the present invention has revealed a compound having a novel structure, and that when the compound is applied to an organic electronic element, the luminous efficiency, stability and lifetime of the element are greatly improved.

Accordingly, it is an object of the present invention to provide a novel compound, an organic electronic element using the same, and an electronic device.

Technical Solution

The present invention provides a compound represented by Formula 1:

In another aspect, the present invention provides an organic electronic device including the compound represented by Formula 1 and an electronic device thereof.

Effects of the Invention

By using the compound according to the present invention, it is possible to achieve a high luminous efficiency, a low driving voltage, and a high heat resistance of the element, and can greatly improve the color purity and lifetime of the element.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 to FIG. 3 each illustrate an example organic electronic element according to one aspect of the present invention.

FIG. 4 shows the formula of a compound according to one aspect of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

Hereinafter, several embodiments of the present invention will be described in detail. In the following, a detailed description of known functions and configurations of an organic electric element or device which are incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear. Terms, such as first, second, A, B, (a), (b) or the like may be used herein when describing components of the present invention. Each of these terminologies is not used to define an essence, order or sequence of a corresponding component but used merely to distinguish the corresponding component from other component(s). It should be noted that if a component is described as being “connected”, “coupled”, or “connected” to another component, the component may be directly connected or connected to the other component, but another component may be “connected”, “coupled” or “connected” between each component.

Unless otherwise stated, the following is the meaning of the terms used in the specification and the accompanying claims.

Unless otherwise stated, the term “halo” or “halogen”, as used herein, includes fluorine, bromine, chlorine, or iodine.

Unless otherwise stated, the term “alkyl” or “alkyl group”, as used herein, has a single bond of 1 to 60 carbon atoms, and means saturated aliphatic functional radicals including a linear alkyl group, a branched chain alkyl group, a cycloalkyl group (alicyclic), an cycloalkyl group substituted with a alkyl or an alkyl group substituted with a cycloalkyl.

Unless otherwise stated, the term “alkenyl” or “alkynyl”, as used herein, has double or triple bonds of 2 to 60 carbon atoms, but is not limited thereto, and includes a linear or a branched chain group.

Unless otherwise stated, the term “cycloalkyl”, as used herein, means alkyl forming a ring having 3 to 60 carbon atoms, but is not limited thereto.

Unless otherwise stated, the term “alkoxyl group”, “alkoxy group” or “alkyloxy group”, as used herein, means an oxygen radical attached to an alkyl group, but is not limited thereto, and has 1 to 60 carbon atoms.

Unless otherwise stated, the term “aryloxyl group” or “aryloxy group”, as used herein, means an oxygen radical attached to an aryl group, but is not limited thereto, and has 6 to 60 carbon atoms.

Unless otherwise stated, the term “aryl group” or “arylene group”, as used herein, has 6 to 60 carbon atoms, but is not limited thereto. Herein, the aryl group or arylene group means a monocyclic and polycyclic aromatic group, and may also be formed in conjunction with an adjacent group. Examples of “aryl group” may include a phenyl group, a biphenyl group, a fluorene group, or a spirofluorene group.

The prefix “aryl” or “ar” means a radical substituted with an aryl group. For example, an arylalkyl may be an alkyl substituted with an aryl, and an arylalenyl may be an alkenyl substituted with aryl, and a radical substituted with an aryl has a number of carbon atoms as defined herein.

Also, when prefixes are named subsequently, it means that substituents are listed in the order described first. For example, an arylalkoxy means an alkoxy substituted with an aryl, an alkoxylcarbonyl means a carbonyl substituted with an alkoxyl, and an arylcarbonylalkenyl also means an alkenyl substituted with an arylcarbonyl, wherein the arylcarbonyl may be a carbonyl substituted with an aryl.

Unless otherwise stated, the term “heterocyclic group”, as used herein, contains one or more heteroatoms, but is not limited thereto, has 2 to 60 carbon atoms, includes any one of monocyclic and polycyclic rings, and may include heteroaliphadic ring and/or heteroaromatic ring. Also, the heterocyclic group may also be formed in conjunction with an adjacent group.

Unless otherwise stated, the term “heteroatom”, as used herein, represents at least one of N, O, S, P, or Si.

Also, the term “heterocyclic group” may include a ring including SO₂ instead of carbon consisting of cycle. For example, “heterocyclic group” includes compound below.

Unless otherwise stated, the term “fluorenyl group” or “fluorenylene group”, as used herein, means a monovalent or divalent functional group, in which R, R′ and R″ are all hydrogen in the following structures, and the term “substituted fluorenyl group” or “substituted fluorenylene group” means that at least one of the substituents R, R′, R″ is a substituent other than hydrogen, and include those in which R and R′ are bonded to each other to form a spiro compound together with the carbon to which they are bonded.

The term “spiro compound”, as used herein, has a ‘spiro union’, and a spiro union means a connection in which two rings share only one atom. At this time, atoms shared in the two rings are called ‘spiro atoms’, and these compounds are called ‘monospiro’, ‘di-spiro’ and ‘tri-spiro-’, respectively, depending on the number of atoms in a compound.

Unless otherwise stated, the term “aliphatic”, as used herein, means an aliphatic hydrocarbon having 1 to 60 carbon atoms, and the term “aliphatic ring”, as used herein, means an aliphatic hydrocarbon ring having 3 to 60 carbon atoms.

Unless otherwise stated, the term “ring”, as used herein, means an aliphatic ring having 3 to 60 carbon atoms, or an aromatic ring having 6 to 60 carbon atoms, or a hetero ring having 2 to 60 carbon atoms, or a fused ring formed by the combination of them, and includes a saturated or unsaturated ring.

Other hetero compounds or hetero radicals other than the above-mentioned hetero compounds include, but are not limited thereto, one or more heteroatoms.

Unless otherwise stated, the term “substituted or unsubstituted”, as used herein, means that substitution is substituted by at least one substituent selected from the group consisting of, but is not limited thereto, deuterium, halogen, an amino group, a nitrile group, a nitro group, a C₁-C₂₀ alkyl group, a C₁-C₂₀ alkoxyl group, a C₁-C₂₀ alkylamine group, a C₁-C₂₀ alkylthiopen group, a C₆-C₂₀ arylthiopen group, a C₂-C₂₀ alkenyl group, a C₂-C₂₀ alkynyl group, a C₃-C₂₀ cycloalkyl group, a C₆-C₂₀ aryl group, a C₆-C₂₀ aryl group substituted by deuterium, a C₈-C₂₀ arylalkenyl group, a silane group, a boron group, a germanium group, and a C₂-C₂₀ heterocyclic group.

Unless otherwise expressly stated, the Formula used in the present invention, as used herein, is applied in the same manner as the substituent definition according to the definition of the exponent of the following Formula.

wherein, when a is an integer of zero, the substituent R¹ is absent, when a is an integer of 1, the sole substituent R¹ is linked to any one of the carbon constituting the benzene ring, when a is an integer of 2 or 3, each substituent R¹s may be the same and different, when a is an integer of 4 to 6, and is linked to the benzene ring in a similar manner, whereas the indication of hydrogen bound to the carbon forming the benzene ring is omitted.

Hereinafter, a compound according to an aspect of the present invention and an organic electronic element comprising the same will be described.

One aspect of the present invention is to provide a compound represented by Formula 1:

In Formula 1, each symbol may be defined as follows:

1) X¹, X², X³, X⁴ and X⁵ are each independently O or S, 2) a, b, c and d are each independently an integer of 0 to 4, a+b+c+d is 1 or more, 3) e, f, g, h, i, j, k and l are each independently an integer of 0 to 4, wherein in case e, f, g, h, i, j, k and l are 2 or more, R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are each in plural being the same or different, and an adjacent plurality of R¹ or a plurality of R² or a plurality of R³ or a plurality of R⁴ or a plurality of R⁵ or a plurality of R⁶ or a plurality of R⁷ or a plurality of R⁸ may be bonded to each other to form a ring, 4) m, n, o and p are each independently an integer of 0 to 3, m+n+o+p is 1 or more, 5) L¹, L², L³, L⁴, L⁵, L⁶, L⁷ and L⁸ are the same or different from each other, and are each independently selected from the group consisting of single bond; a C₆-C₆₀ arylene group; a fluorenylene group; a fused ring group of a C₃-C₆₀ aliphatic ring and a C₆-C₆₀ aromatic ring; a C₂-C₆₀ heterocyclic group; wherein in case L¹, L², L³, L⁴, L⁵, L⁶, L⁷ and L⁸ are an arylene group, it is preferably an C₆˜C₃₆ arylene group, more preferably an C₆˜C₂₄ arylene group, when L¹, L², L³, L⁴, L⁵, L⁶, L⁷ and L⁸ are a fused ring group, it is preferably a fused ring group of an C₆˜C₃₆ aliphatic ring and an C₆˜C₃₆ aromatic ring, and more preferably a fused ring group of an C₆˜C₂₄ aliphatic ring and an C₆˜C₂₄ aromatic ring, when L¹, L², L³, L⁴, L⁵, L⁶, L⁷ and L⁸ are a heterocyclic group, it is preferably a C₂˜C₃₆ heterocyclic group, and more preferably a C₂˜C₂₄ heterocyclic group. 6) Ar¹, Ar³, Ar⁵ and Ar⁷ are the same or different from each other, and are each independently selected from the group consisting of hydrogen; deuterium; tritium; halogen; cyano group; nitro group; C₆-C₆₀ aryl group; a fluorenyl group; a C₂-C₆₀ heterocyclic group including at least one heteroatom of O, N, S, Si or P; a fused ring group of a C₃-C₆₀ aliphatic ring and a C₆-C₆₀ aromatic ring; C₁-C₅₀ alkyl group; C₂-C₂₀ alkenyl group; C₂-C₂₀ alkynyl group; C₁-C₃₀ alkoxyl group; C₆-C₃₀ aryloxy group; and -L′-N(R_(a))(R_(b)); wherein in case Ar¹, Ar³, Ar⁵ and Ar⁷ are an aryl group, it is preferably an C₆˜C₃₆ aryl group, more preferably an C₆˜C₂₅ aryl group, in case Ar¹, Ar³, Ar⁵ and Ar⁷ are an heterocyclic group, it is preferably a C₂˜C₃₆ heterocyclic group, and more preferably a C₂˜C₂₄ heterocyclic group, in case Ar¹, Ar³, Ar⁵ and Ar⁷ are a fused ring group, it is preferably a fused ring group of an C₆˜C₃₆ aliphatic ring and an C₆˜C₃₆ aromatic ring, more preferably a fused ring group of an C₆˜C₂₄ aliphatic ring and an C₆˜C₂₄ aromatic ring, in case Ar¹, Ar³, Ar⁵ and Ar⁷ are alkyl groups, it is preferably an C₁˜C₃₆ alkyl group, more preferably an C₁˜C₂₄ alkyl group, 7) Ar², Ar⁴, Ar⁶ and Ar⁸ are each independently selected from the group consisting of a C₆-C₆₀ aryl group; a fluorenyl group; a C₂-C₆₀ heterocyclic group including at least one heteroatom of O, N, S, Si or P; a fused ring group of a C₃-C₆₀ aliphatic ring and a C₆-C₆₀ aromatic ring; -L⁹-Ar′; wherein in case Ar², Ar⁴, Ar⁶ and Ar⁸ are an aryl group, it is preferably an C₆˜C₃₆ aryl group, more preferably an C₆˜C₂₅ aryl group, in case Ar², Ar⁴, Ar⁶ and Ar⁸ are heterocyclic groups, it is preferably a C₂˜C₃₆ heterocyclic group, and more preferably a C₂˜C₂₄ heterocyclic group, in case Ar², Ar⁴, Ar⁶ and Ar⁸ are a fused ring group, it is preferably a fused ring group of an C₆˜C₃₆ aliphatic ring and an C₆˜C₃₆ aromatic ring, more preferably a fused ring group of an C₆˜C₂₄ aliphatic ring and an C₆˜C₂₄ aromatic ring. 8) wherein L⁹ is selected from the group consisting of single bond; a C₆-C₆₀ arylene group; a fluorenylene group; a fused ring group of a C₃-C₆₀ aliphatic ring and a C₆-C₆₀ aromatic ring; a C₂-C₆₀ heterocyclic group; Ar′ is selected from a C₆-C₆₀ aryl group; a fluorenylene group; a C₂-C₆₀ heterocyclic group including at least one heteroatom of O, N, S, Si or P; a fused ring group of a C₃-C₆₀ aliphatic ring and a C₆-C₆₀ aromatic ring; wherein in case L⁹ is arylene group, it is preferably an C₆˜C₃₆ arylene group, more preferably an C₆˜C₂₄ arylene group, when L⁹ is a fused ring group, it is preferably a fused ring group of an C₆˜C₃₆ aliphatic ring and an C₆˜C₃₆ aromatic ring, and more preferably a fused ring group of an C₆˜C₂₄ aliphatic ring and an C₆˜C₂₄ aromatic ring, when L⁹ is a heterocyclic group, it is preferably a C₂˜C₃₆ heterocyclic group, and more preferably a C₂˜C₂₄ heterocyclic group.

wherein in case Ar′ is an aryl group, it is preferably an C₆˜C₃₆ aryl group, more preferably an C₆˜C₂₅ aryl group, in case Ar′ is a heterocyclic group, it is preferably C₂˜C₃₆ heterocyclic groups, and more preferably C₂˜C₂₄ heterocyclic groups, in case Ar′ is a fused ring group, it is preferably a fused ring group of an C₆˜C₃₆ aliphatic ring and an C₆˜C₃₆ aromatic ring, more preferably a fused ring group of an C₆˜C₂₄ aliphatic ring and an C₆˜C₂₄ aromatic ring.

9) R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are the same or different from each other, and are each independently selected from the group consisting of hydrogen; deuterium; tritium; halogen; cyano group; nitro group; C₆-C₆₀ aryl group; a fluorenyl group; a C₂-C₆₀ heterocyclic group including at least one heteroatom of O, N, S, Si or P; a fused ring group of a C₃-C₆₀ aliphatic ring and a C₆-C₆₀ aromatic ring; C₁-C₅₀ alkyl group; C₂-C₂₀ alkenyl group; C₂-C₂₀ alkynyl group; C₁-C₃₀ alkoxyl group; C₆-C₃₀ aryloxy group; and -L′-N(R_(a))(R_(b)); wherein in case R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are an aryl group, it is preferably an C₆˜C₃₆ aryl group, more preferably an C₆˜C₂₅ aryl group, in case R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are an heterocyclic group, it is preferably a C₂˜C₃₆ heterocyclic group including at least one heteroatom of O, N, S, Si or P; in case R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are a fused ring group, it is preferably a fused ring group of an C₆˜C₃₆ aliphatic ring and an C₆˜C₃₆ aromatic ring, more preferably a fused ring group of an C₆˜C₂₄ aliphatic ring and an C₆˜C₂₄ aromatic ring.

10) wherein L′ is selected from the group consisting of a single bond; a C₆-C₆₀ arylene group; a fluorenylene group; C₃-C₆₀ aliphatic ring; a C₂-C₆₀ heterocyclic group including at least one heteroatom of O, N, S, Si or P; a combination thereof; wherein R_(a) and R_(b) are each independently selected from the group consisting of a C₆-C₆₀ aryl group; a fluorenyl group; C₃-C₆₀ aliphatic ring; a C₂-C₆₀ heterocyclic group including at least one heteroatom of O, N, S, Si or P;

wherein in case L′ is an arylene group, it is preferably an C₆˜C₃₆ arylene group, more preferably an C₆˜C₂₄ arylene group, in case L′ is an aliphatic ring, it is preferably a C₃˜C₃₆ aliphatic ring, more preferably C₆˜C₂₄ aliphatic ring, when L′ is a heterocyclic group, it is preferably a C₂˜C₃₆ heterocyclic group including at least one heteroatom of O, N, S, Si or P; and more preferably a C₂˜C₂₄ heterocyclic group, wherein in case R_(a) and R_(b) are an aryl group, it is preferably an C₆˜C₃₆ aryl group, more preferably an C₆˜C₂₅ aryl group, in case R_(a) and R_(b) are an aliphatic ring, it is preferably a C₃˜C₃₆ aliphatic ring, more preferably C₃˜C₂₄ aliphatic ring, in case R_(a) and R_(b) are a heterocyclic group, it is preferably a C₂˜C₃₆ heterocyclic group including at least one heteroatom of O, N, S, Si or P; and more preferably a C₂˜C₂₄ heterocyclic group including at least one heteroatom of O, N, S, Si or P; 11) wherein, the aryl group, arylene group, heterocyclic group, fluorenyl group, fluorenylene group, fused ring group, alkyl group, alkenyl group, alkoxy group and aryloxy group may be substituted with one or more substituents selected from the group consisting of deuterium; halogen; silane group; siloxane group; boron group; germanium group; cyano group; nitro group; C₁-C₂₀ alkylthio group; C₁-C₂₀ alkoxyl group; C₁-C₂₀ alkyl group; C₂-C₂₀ alkenyl group; C₂-C₂₀ alkynyl group; C₆-C₂₅ aryl group; C₆-C₂₅ aryl group substituted with deuterium; a fluorenyl group; C₂˜C₂₀ heterocyclic group; C₃-C₂₀ cycloalkyl group; C₇-C₂₀ arylalkyl group; C₈-C₂₀ arylalkenyl group; and -L′-N(R_(a))(R_(b)); the substituents may combine each other to form a saturated or unsaturated ring selected from the group consisting of a C₃-C₆₀ aliphatic ring, a C₆-C₆₀ aromatic ring, a C₂-C₆₀ heterocyclic group, a fused ring formed by combination thereof.

In one embodiment, Formula 1 includes a compound represented by any one of Formulas 1-1 to 1-9:

In Formulas 1-1 to 1-9,

X¹, X², X³, X⁴, X⁵ and R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸ and L¹, L², L³, L⁴, L⁵, L⁶, L⁷, L⁸ and e, f, g, h, i, j, k, l, m, n, o and p are the same as defined for those in Formula 1.

In another embodiment, Formula 1 includes a compound represented by Formula 2:

In Formula 2,

X¹, X², X³, X⁴, X⁵ and R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸ and L¹, L², L³, L⁴, L⁵, L⁶, L⁷, L⁸ and Ar¹, Ar², Ar³, Ar⁴, Ar⁵, Ar⁶, Ar⁷, and Ar⁸, and a, b, c, d, e, f, g, h, i, j, k, l and n are the same as defined for those in Formula 1.

In another embodiment, Formula 1 includes a compound represented by any one of Formulas 2-1 to 2-4:

In Formulas 2-1 to 2-4,

X¹, X³, R¹, R², R³, R⁴, R⁶, L³, L⁴, Ar³, Ar⁴, e, f, g, h, j and n are the same as defined in Formula 1.

In another embodiment, Formula 1 includes a compound represented by Formula 3:

In Formula 3,

1) X¹, X³, R¹, R², R³, R⁴, R⁶, L³, L⁴, Ar⁴, e, f, g, h

j are the same as defined in Formula 1, 2) Ar^(3a) is selected from the group consisting of deuterium; tritium; halogen; cyano group; nitro group; C₆-C₆₀ aryl group; a fluorenyl group; a C₂-C₆₀ heterocyclic group including at least one heteroatom of O, N, S, Si or a fused ring group of a C₃-C₆₀ aliphatic ring and a C₆-C₆₀ aromatic ring; C₁-C₅₀ alkyl group; C₂-C₂₀ alkenyl group; C₂-C₂₀ alkynyl group; C₁-C₃₀ alkoxyl group; C₆-C₃₀ aryloxy group; and -L′-N(R_(a))(R_(b)).

In another embodiment, Formula 1 includes a compound represented by Formula 4:

In Formula 4,

1) X¹, X³, R¹, R², R³, R⁴, R⁶, L³, L⁴, L⁹, Ar³, e, f, g, h, j and n are the same as defined in Formula 1, 2) X⁶ and X⁷ are each independently a single bone, CR′R″, O or S, except that X⁶ and X⁷ are a single bond at the same time, 3) R′ and R″ are each independently a hydrogen; C₆-C₆₀ aryl group; a fluorenyl group; a C₃-C₆₀ heterocyclic group; C₁-C₅₀ alkyl group; C₂-C₆₀ alkenyl group; or C₆-C₆₀ aryloxy group; R′ and R″ are bonded to each other to form a C₆-C₆₀ aromatic ring; fluorenyl group; a C₂-C₆₀ heterocyclic group including at least one heteroatom of O, N, S, Si or C₃-C₆₀ aliphatic ring; or a fused ring group of a C₃-C₆₀ aliphatic ring and a C₆-C₆₀ aromatic ring, wherein in case R′ and R″ are an aryl group, it is preferably an C₆˜C₃₆ aryl group, more preferably an C₆˜C₂₅ aryl group, in case R′ and R″ are a heterocyclic group, it is preferably C₂˜C₃₆ heterocyclic groups, and more preferably C₂˜C₂₄ heterocyclic groups, in case R′ and R″ are an alkyl group, it is preferably C₁-C₃₆ alkyl group, and more preferably C₁-C₂₄ alkyl group, in case R′ and R″ are an alkenyl group, it is preferably a C₂-C₃₆ alkenyl group, and more preferably a C₂-C₂₄ alkenyl group, in case R′ and R″ are an aryloxy group, it is preferably C₆-C₃₆ aryloxy group, and more C₆-C₂₄ aryloxy group. 4) R⁹ and R¹⁰ are the same as the definition of R¹ in Formula 1, 5) q is an integer of 0 to 3, r is an integer of 0 to 4.

In another embodiment, Formula 1 includes a compound represented by Formula 4-1.

In Formula 4-1,

1) X¹, X³, R¹, R², R³, R⁴, R⁶, L³, L⁴, L⁹, Ar³, e, f, g, h, j and n are the same as defined in Formula 1, 2) R⁹, R¹⁰, R′, R″, q and r are the same as defined in Formula 4, 3) Z is a single bond, O or S.

In another embodiment, Formula 1 includes a compound represented by Formula 4-2:

In Formula 4-2,

1) X¹, X³, R¹, R², R³, R⁴, R⁶, L³, L⁴, L⁹, Ar³, e, f, g, h, j and n are the same as defined in Formula 1, 2) R⁹, R¹⁰, R′, R″, q and r are the same as defined in Formula 4.

In another embodiment, Formula 1 includes a compound represented by any one of Formulas 5-1 to 5-4:

In Formulas 5-1 to 5-4,

1) X¹, X³, R¹, R², R³, R⁴, R⁶, L³, L⁴, Ar³, e, f, g, h, j and n are the same as defined in Formula 1, 2) R⁹, R¹⁰, R′, R″, q and r are the same as defined in Formula 4.

In another embodiment, Formula 1 includes a compound represented by Formula 6-1.

In Formula 6-1,

1) X¹, X³, R¹, R², R³, R⁴, R⁶, L³, L⁴, L⁹, Ar³, e, f, g, h, j and n are the same as defined in Formula 1, 2) R⁹, R¹⁰, q and r are the same as defined in Formula 4,

3) Y¹ is O or S,

4) R¹¹ and R¹² are the same as the definition of R¹ in Formula 1, 5) s and t are each independently an integer of 0 to 4.

In another embodiment, Formula 1 includes a compound represented by Formula 6-2:

In Formula 6-2,

1) X¹, X³, R¹, R², R³, R⁴, R⁶, L³, L⁴, Ar³, e, f, g, h, j and n are the same as defined in Formula 1, 2) R⁹, R¹⁰, q and r are the same as defined in Formula 4, 3) Y¹, R¹¹, R¹², s and t are the same as defined in Formula 6-1.

In another embodiment, Formula 1 includes a compound represented by Formula 6-3:

In Formula 6-3,

1) X¹, X³, R¹, R², R³, R⁴, R⁶, L³, L⁴, Ar³, e, f, g, h, j and n are the same as defined in Formula 1, 2) R⁹, R¹⁰, q and r are the same as defined in Formula 4, 3) Y¹, R¹¹, R¹², s and t are the same as defined in Formula 6-1.

Specifically, the compound represented by Formula 1 may be a compound represented by any one of Compounds P-1 to P-139, but it is not limited thereto:

More specifically, the compound represented by Formula 1 may be a compound represented by any one of the following compounds P1-1 to P1-86, but is not limited thereto:

Also, the compound represented by Formula 1 may be a compound represented by any one of the following compounds P2-1 to P2-55, but is not limited thereto:

The present invention also provides a compound represented by Formula 7:

In Formula 7,

1) R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷ and R²⁸ are the same as or different each other and are each independently selected from the group consisting of hydrogen; deuterium; halogen; cyano group; nitro group; C₆-C₆₀ aryl group; a fluorenyl group; a C₂-C₆₀ heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si or a fused ring group of a C₃-C₆₀ aliphatic ring and a C₆-C₆₀ aromatic ring; a C₁-C₆₀ alkyl group; a C₂-C₆₀ alkenyl group; a C₂-C₆₀ alkynyl group; a C₁-C₆₀ alkoxy group; and a C₆-C₆₀ aryloxy group; or a plurality of adjacent R²¹s, or a plurality of R²²s, or a plurality of R²³s, or a plurality of R²⁴s, or a plurality of R²⁵s, or a plurality of R²⁶s, or a plurality of R²⁷s, or a plurality of R²⁸s can be bonded to each other to form a ring, 2) W¹ and W² are each independently O or S, 3) L¹¹ is a single bond; a C₆-C₆₀ arylene group; a fluorenylene group; a C₂-C₆₀ heterocyclic group containing at least one hetero atom of O, N, S, Si or a fused ring group of a C₃-C₆₀ aliphatic ring and a C₆-C₆₀ aromatic ring; 4) Ar¹¹ is a C₆-C₆₀ aryl group; 5) a1, a3, a4, a6, a7 and a8 are each independently an integer of 0 to 4, a2 and a5 are each independently an integer of 0 to 3, 6) wherein, the aryl group, arylene group, heterocyclic group, fluorenyl group, fluorenylene group, aliphatic ring group, fused ring group, alkyl group, alkenyl group, alkynyl group, alkoxyl group and aryloxy group may be substituted with one or more substituents selected from the group consisting of deuterium; halogen; a silane group; siloxane group; boron group; germanium group; cyano group; nitro group; a C₁-C₂₀ alkylthio group; C₁-C₂₀ alkoxy group; C₁-C₂₀ alkyl group; C₂-C₂₀ alkenyl group; C₂-C₂₀ alkynyl group; C₆-C₂₀ aryl group; C₆-C₂₀ aryl group substituted with deuterium; a fluorenyl group; C₂-C₂₀ heterocyclic group; C₃-C₂₀ cycloalkyl group; C₇-C₂₀ arylalkyl group and C₈-C₂₀ arylalkenyl group, wherein the substituents may be bonded to each other to form a saturated or unsaturated ring, wherein the term ‘ring’ means a C₃-C₆₀ aliphatic ring or a C₆-C₆₀ aromatic ring or a C₂-C₆₀ heterocyclic group or a fused ring formed by the combination thereof.

In one embodiment, Formula 7 is represented by one of Formulas 7-1 to 7-3:

In Formulas 7-1 to 7-3, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷ and R²⁸, W¹, W², L¹¹, Ar¹¹, and a¹, a², a³, a⁴, a⁵, a⁶, a⁷ and a⁸ are the same as defined for those in Formula 7.

In one embodiment, L¹¹ of Formula 7 is represented by one of Formulas a-1 to a-5:

In Formulas a-1 to a-5,

1) R³⁰, R³¹, R³², R³³, R³⁴, R³⁵, R³⁶ and R³⁷ are the same as the definition of R²¹, 2) b1, b3, b4 and b8 are each independently an integer of 0 to 4, b2 is an integer of 0 to 6, b5 and b6 are each independently an integer of 0 to 3, and b7 is an integer of 0 to 2,

3) Z¹ is O or S,

4) * means a position bonded to N (nitrogen) in Formula 7, and *2 means a position bonded to Ar¹¹ in Formula 7.

In another embodiment, L¹¹ is represented by one of Formulas a-6 to a-46:

In Formulas a-6 to a-46, R³⁰, R³¹, R³², R³³, R³⁴, R³⁵, R³⁶ and R³⁷, b1, b2, b3, b4, b5, b6, b7, b8, Z¹, * and *2 are the same as defined above.

In another embodiment, Formula 7 is represented by Formula 7-4 or Formula 7-5:

In Formula 7-4 and Formula 7-5,

1) R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷ and R²⁸ are the same as defined above, 2) R³⁰, R³⁴, R³⁵, b1, b5, b6 and Z¹ are the same as defined above.

In another embodiment, Formula 7 is represented by Formula 7-6:

In Formula 7-6,

1) R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷ and R²⁸, a1, a2, a3, a4, a5, a6, a7 and a8, W¹ and W² are the same as defined above, 2) R³⁰ and b1 are the same as the defined above, 3) R⁴⁰ is the same as the definition of R²¹, 4) c1 is an integer of 0 to 5.

In another embodiment, Formula 7 is represented by Formula 7-7:

In Formula 7-7,

1) R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷ and R²⁸, a1, a2, a3, a4, a5, a6, a7 and a8, W¹ and W² are the same as defined above, 2) R³⁰ and b1 are the same as defined above, 3) R⁴⁰ is the same as the definition of R²¹, 4) c1 is an integer of 0 to 5.

In another embodiment, Formula 7 is preferably represented by Formula 7-8:

In Formula 7-8, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R³⁰ and R⁴⁰, a1, a2, a3, a4, a5, a6, a7 and a8, 131, c1, W¹ and W² are the same as defined above.

In another embodiment, Formula 7 is preferably represented by one of Formulas 7-9 to 7-11:

In Formulas 7-9 to 7-11, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R³⁴ and R³⁵, a1, a2, a3, a4, a5, a6, a7 and a8, b5, b6, W¹, W², Ar¹¹ and Z¹ are defined the same as above.

In another embodiment, Formula 7 is preferably represented by Formula 7-12:

In Formula 7-12, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R³⁴, R³⁵ and R⁴⁰, a1, a2, a3, a4, a5, a6, a7 and a8, b5, b6, c1, W¹, W², Ar¹¹ and Z¹ are the same as defined above.

A non-limiting example of the compound of Formula 7 includes Compounds P2-46, P2-47, and P3-1 to P3-40:

Referring to FIG. 1, the organic electronic element (100) according to the present invention includes a first electrode (110), a second electrode (170), an organic material layer comprising one or more compounds represented by Formula 1 or 2 or 7 between the first electrode (110) and the second electrode (170). Here, the first electrode (110) may be an anode or a positive electrode, and the second electrode (170) may be a cathode or a negative electrode. In the case of an inverted organic electronic element, the first electrode may be a cathode, and the second electrode may be an anode.

The organic material layer may sequentially include a hole injection layer (120), a hole transport layer (130), an emitting layer (140), an electron transport layer (150), and an electron injection layer (160) formed in sequence on the first electrode (110). Here, the remaining layers except the emitting layer (140) may not be formed. The organic material layer may further include a hole blocking layer, an electron blocking layer, an emitting-auxiliary layer (220), a buffer layer (210), etc., and the electron transport layer (150) and the like may serve as a hole blocking layer. (see FIG. 2)

Also, the organic electronic element according to an embodiment of the present invention may further include a protective layer or a light efficiency enhancing layer (180). The light efficiency enhancing layer may be formed on a surface not in contact with the organic material layer among both surfaces of the first electrode or on a surface not in contact with the organic material layer among both surfaces of the second electrode. The compound according to an embodiment of the present invention applied to the organic material layer may be used as a material for a hole injection layer (120), a hole transport layer (130), an emitting-auxiliary layer (220), an electron transport auxiliary layer, an electron transport layer (150), an electron injection layer (160), a host or dopant of an emitting layer (140) or the light efficiency enhancing layer. Preferably, for example, the compound according to Formula 1 or 7 of the present invention may be used as a material for the emitting-auxiliary layer. Another aspect of the present invention is to provide an organic electronic element comprising a first electrode (e.g., anode), a second electrode (e.g., cathode), and an organic material layer formed between the first and second electrodes, wherein the organic material layer comprises a compound represented by Formula 7.

Particularly, the organic material layer may comprise at least one of a hole injection layer, a hole transport layer, an emitting auxiliary layer, an emitting layer, an electron transport auxiliary layer, an electron transport layer, and an electron injection layer. In one embodiment, the organic material layer may be preferably an emitting auxiliary layer. In another embodiment, the organic material layer may comprise an emitting layer, a hole transport layer which may be formed between the first electrode and the emitting layer, and a plurality of emitting auxiliary layers which may be formed between the hole transport layer and the emitting layer. At least one of the plural emitting auxiliary layers may comprise a compound represented by Formula 7. In one embodiment, the plural emitting auxiliary layers may comprise a first emitting auxiliary layer which is formed adjacent to the hole transport layer, and a second emitting auxiliary layer which is formed adjacent to the emitting layer. The compound of Formula 7 according to one aspect of the present invention may be comprised in the first emitting auxiliary layer, and/or the second emitting auxiliary layer. The organic material layer may include 2 or more stacks including a hole transport layer, an emitting layer, and an electron transport layer sequentially formed on the anode, and may further include a charge generation layer formed between the 2 or more stacks (see FIG. 3). In one embodiment, the organic material layer further comprises a charge generation layer formed between the 2 or more stacks of layers.

Otherwise, even if the same core is used, the band gap, the electrical characteristics, the interface characteristics, and the like may vary depending on which substituent is bonded at which position, therefore the choice of core and the combination of sub-substituents associated therewith is also very important, and in particular, when the optimal combination of energy levels and T1 values and unique properties of materials (mobility, interfacial characteristics, etc.) of each organic material layer is achieved, a long life span and high efficiency can be achieved at the same time.

The organic electroluminescent device according to an embodiment of the present invention may be manufactured using a PVD (physical vapor deposition) method. For example, a metal or a metal oxide having conductivity or an alloy thereof is deposited on a substrate to form a cathode, and the organic material layer including the hole injection layer (120), the hole transport layer (130), the emitting layer (140), the electron transport layer (150), and the electron injection layer (160) is formed thereon, and then depositing a material usable as a cathode thereon can manufacture an organic electroluminescent device according to an embodiment of the present invention.

Also, the present invention provides the organic electronic element wherein the organic material layer is formed by one of a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process or a roll-to-roll process, and the organic material layer provides an organic electronic element comprising the compound as an electron transport material.

As another specific example, the present invention provides an organic electronic element that is used by mixing the same or different compounds of the compound represented by Formula 1 or 7 to the organic material layer.

In another aspect, the present invention provides an emitting-auxiliary layer composition comprising a compound represented by Formula 1 or 7, and provides an organic electronic element comprising the emitting-auxiliary layer.

The present invention also provides an electronic device comprising a display device including the organic electronic element; and a control unit for driving the display device.

According to another aspect, the present invention provides an display device wherein the organic electronic element is at least one of an OLED, an organic solar cell, an organic photo conductor, an organic transistor (organic TFT) and an element for monochromic or white illumination. Here, the electronic device may be a wired/wireless communication terminal which is currently used or will be used in the future, and covers all kinds of electronic devices including a mobile communication terminal such as a cellular phone, a personal digital assistant (PDA), an electronic dictionary, a point-to-multipoint (PMP), a remote controller, a navigation unit, a game player, various kinds of TVs, and various kinds of computers.

Hereinafter, Synthesis Examples of the compound represented by Formula 1 or 7 of the present invention and preparation examples of the organic electronic element of the present invention will be described in detail by way of example, but are not limited to the following examples.

Synthesis Example 1

The compound (Final product) represented by Formula 1 according to the present invention may be prepared by reacting as in Scheme 1 below, but is not limited thereto.

In Reaction Scheme 1,

1) X¹, X², X³, X⁴, X⁵, R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸, L¹, L², L³, L⁴, L⁵, L⁶, L⁷ and L⁸, Ar¹, Ar², Ar³, Ar⁴, Ar⁵, Ar⁶, Ar⁷, and Ar⁸, and a to P are the same as defined above,

2) Hal¹ to Hal⁴ are each independently Br or Cl, 3) a′ to d′ are each independently 0 or 1, at least one of a′ to d′ is 1, 4) Y is the same as the definition of X¹, X², X³, X⁴, X⁵, 5) Ar¹′ is the same as the definition of Ar¹, Ar³, Ar⁵ or Ar⁷, 6) Ar²′ is the same as the definition of Ar², Ar⁴, Ar⁶ or Ar⁸, 7) R¹′ is the same as the definition of R⁵, R⁶, R⁷, R⁸, 8) L¹′ is the same as the definition of L², L⁴, L⁶ or L⁸, 9) e′ is an integer of 0 to 3, f′ is an integer of 0 to 4.

The compound represented by Formula 7 according to the present invention (Final product 2) may be prepared by reacting the compounds as shown in Scheme 1-1, but it is not limited thereto.

I. Synthesis of Sub 1

Sub 1 of Reaction Scheme 1 may be synthesized by the reaction path of Scheme 2 below, but is not limited thereto. When X¹ is —OH, the synthesis path of (1) of Reaction Scheme 2 is followed, and when X¹ is —SH, the synthesis path of (2) of Reaction Scheme 2 is followed.

In Reaction Scheme 2,

X¹, R¹, R², R³, R⁴, e, f, g, h, Hal¹, Hal², Hal³, Har⁴, and a′, b′, c′, d′ are the same as defined in Formula 1.

Synthesis examples of specific compounds belonging to Sub 1 are as follows.

1. Synthesis Example of Sub 1-1

(1) Synthesis Example of Sub 1-1-a

5-Chloro-2-Iodobenzoic Acid (50.0 g, 177 Mmol), Phenol (33.3 g, 354 Mmol), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) (80.9 g, 531 mmol), pyridine (2.9 mL), Copper powder (1.5 g, 23 mmol), CuI (1.5 g, 7.97 mmol) were placed in a round bottom flask, and DMF (1.2 L) was added, followed by refluxing for 3 hours. When the reaction is complete, cool to room temperature and add 3M HCl until precipitation is complete. Thereafter, the precipitate was washed with water and dried to obtain 38.3 g (yield 87%) of the product.

(2) Synthesis Example of Sub 1-1-b

Sub 1-1-a (38.3 g, 154 mmol) obtained in the above synthesis was added to a round bottom flask, and H₂SO₄ (1.1 mL, 21.5 mmol) was added, followed by refluxing until all the starting materials were dissolved. When all the starting materials are dissolved, cool to room temperature and add ice water to precipitate. Thereafter, the precipitate was washed with water, dried, dissolved in CH₂Cl₂, and recrystallized with a Silicagel column to obtain 23.09 g (yield 65%) of the product.

(3) Synthesis Example of Sub 1-1-c

2-bromo-1,1′-biphenyl (23.3 g, 99.7 mmol) was dissolved in THF (270 mL) in a round bottom flask under a nitrogen atmosphere, and then cooled to −78° C.

Then, n-BuLi (40 mL) was slowly titrated and the mixture was stirred for 30 minutes. Subsequently, Sub 1-1-b (23 g, 99.7 mmol) obtained in the above synthesis was dissolved in THF (140 mL), and then slowly titrated into a reaction round bottom flask. After stirring for an additional 1 hour at −78° C., it is gradually raised to room temperature. When the reaction was completed, the product was extracted with Ethyl acetate and water, and the organic layer was dried over MgSO₄ and concentrated, and the resulting compound was recrystallized in a silica gel column to obtain 32.6 g (yield 85%) of the product.

(4) Synthesis Example of Sub 1-1

Sub 1-1-c (32 g, 84.7 mmol) obtained in the above synthesis, acetic acid (208 mL), and concentrated hydrochloric acid (34.6 mL) were added to a round bottom flask, followed by stirring at 60 to 80° C. for 3 hours under a nitrogen atmosphere. When the reaction was completed, the product was extracted with CH₂Cl₂ and water, and the organic layer was dried over MgSO₄ and concentrated, and the resulting compound was recrystallized with a silica gel column to obtain 27.7 g (91% yield) of the product.

2. Synthesis Example of Sub 1-11

(1) Synthesis Example of Sub 1-11-a

2-iodobenzoic acid (50.0 g, 202 mmol), Thiophenol (22.2 g, 202 mmol), Potassium hydroxide (56.6 g, 1008 mmol), Copper powder (1.3 g, 20.2 mmol) were placed in a round bottom flask and water (1.3 L) was added, followed by refluxing for 12 hours. When the reaction is complete, cool to room temperature and add 3M HCl until precipitation is complete. Thereafter, the precipitate was washed with water and dried to obtain 41.3 g (yield 89%) of the product.

(2) Synthesis Example of Sub 1-11-b

Sub 1-11-a (41.3 g, 179 mmol) and H₂SO₄ (1.3 mL) obtained in the above synthesis was used for the synthesis of Sub 1-1-b to obtain 25.9 g (68% yield) of a product.

(3) Synthesis Example of Sub 1-11-c

2-bromo-4′-chloro-1,1′-biphenyl (32.6 g, 122 mmol), n-BuLi (49 mL), Sub 1-11-b (25.9 g, 122 mmol) obtained in the above synthesis was used for the synthesis of Sub 1-1-c to obtain 40.1 g (82% yield) of a product.

(4) Synthesis Example of Sub 1-11

Sub 1-11-c (40.1 g, 100 mmol) obtained in the above synthesis, acetic acid (250 mL), and concentrated hydrochloric acid (40 mL) were obtained by using the synthesis method of Sub 1-1 above to obtain 31.8 g (yield 83%) of the product.

3. Synthesis Example of Sub 1-20

(1) Synthesis Example of Sub 1-20-a

3-chloro-2-iodobenzoic acid (30.0 g, 106.2 mmol), Thiophenol (11.7 g, 106.2 mmol), Potassium hydroxide (29.8 g, 531 mmol), Copper powder (0.67 g, 10.6 mmol) were used to obtain 23.6 g of a product (84% yield) using the synthesis method of Sub 1-11-a.

(2) Synthesis Example of Sub 1-20-b

Sub 1-20-a (23.6 g, 89.2 mmol) and H₂SO₄ (0.67 mL) obtained in the above synthesis was used for the synthesis of Sub 1-1-b to obtain 14.5 g (66% yield) of a product.

(3) Synthesis Example of Sub 1-20-c

1-(2-bromophenyl)naphthalene (16.6 g, 58.8 mmol), n-BuLi (24 mL), Sub 1-20-b (14.5 g, 58.8 mmol) obtained in the above synthesis was used for the synthesis of Sub 1-1-c to obtain 21.5 g (81% yield) of a product.

(4) Synthesis Example of Sub 1-20

Sub 1-20-c (21 g, 46.6 mmol) obtained in the above synthesis, acetic acid (116 mL), and concentrated hydrochloric acid (19 mL) were obtained by using the synthesis method of Sub 1-1 above to obtain 15.9 g (yield 79%) of the product.

4. Synthesis Example of Sub 1-55

(1) Synthesis Example of Sub 1-55-a

2-iodobenzoic acid (15 g, 60.5 mmol), Sub 1′-55 (37.9 g, 120.1 mmol), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) (27.6 g, 181.4 mmol), pyridine (0.98 mL), Copper powder (0.5 g, 7.9 mmol), CuI (0.5 g, 2.7 mmol) were used to obtain 27.7 g of a product (78% yield) using the synthesis method of Sub 1-1-a.

(2) Synthesis Example of Sub 1-55-b

Sub 1-55-a (27.7 g, 47.1 mmol) and H₂SO₄ (0.35 mL) obtained in the above synthesis was used for the synthesis of Sub 1-1-b to obtain 17.7 g (64% yield) of a product.

(3) Synthesis Example of Sub 1-55-c

2-bromo-2′-chloro-1,1′-biphenyl (7.8 g, 29 mmol), n-BuLi (11.7 mL), Sub 1-55-b (17 g, 29 mmol) obtained in the above synthesis was used for the synthesis of Sub 1-1-c to obtain 17.3 g (77% yield) of a product.

(4) Synthesis Example of Sub 1-55

Sub 1-55-c (17.3 g, 22.3 mmol) obtained in the above synthesis, acetic acid (56 mL), and concentrated hydrochloric acid (9.3 mL) were obtained by using the synthesis method of Sub 1-1 above to obtain 13.5 g (yield 80%) of the product.

5. Synthesis Example of Sub 1-140

(1) Synthesis Example of Sub 1-140-a

3-chloro-2-iodobenzoic acid (18 g, 63.7 mmol), Sub 1′-140 (28.3 g, 63.7 mmol), Potassium hydroxide (17.9 g, 318.6 mmol), Copper powder (0.4 g, 6.4 mmol) were used to obtain 30.1 g of a product (79% yield) using the synthesis method of Sub 1-11-a.

(2) Synthesis Example of Sub 1-140-b

Sub 1-140-a (30.1 g, 46.3 mmol) and H₂SO₄ (0.35 mL) obtained in the above synthesis was used for the synthesis of Sub 1-1-b to obtain 18.1 g (62% yield) of a product.

(3) Synthesis Example of Sub 1-140-c

Sub 1″-140 (19.9 g, 30.3 mmol), n-BuLi (12.2 mL), Sub 1-141-b (18.1 g, 30.3 mmol) obtained in the above synthesis were used for the synthesis of Sub 1-1-c to obtain 24.5 g (70% yield) of a product.

(4) Synthesis Example of Sub 1-140

Sub 1-140-c (24.5 g, 21.1 mmol) obtained in the above synthesis, acetic acid (53 mL), and concentrated hydrochloric acid (8.8 mL) were obtained by using the synthesis method of Sub 1-1 above to obtain 18.1 g (yield 75%) of the product.

6. Synthesis Example of Sub 1-152

(1) Synthesis Example of Sub 1-152-a

4-chloro-2-iodobenzoic acid (12 g, 42.5 mmol), 3-chlorophenol (10.9 g, 84.97 mmol), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) (19.4 g, 127.5 mmol), pyridine (0.69 mL), Copper powder (0.35 g, 5.5 mmol), CuI (0.36 g, 1.9 mmol) were used to obtain 9.7 g of a product (81% yield) using the synthesis method of Sub 1-1-a.

(2) Synthesis Example of Sub 1-152-b

Sub 1-152-a (9.7 g, 34.3 mmol) and H₂SO₄ (0.26 mL) obtained in the above synthesis was used for the synthesis of Sub 1-1-b to obtain 6.6 g (73% yield) of a product.

(3) Synthesis Example of Sub 1-152-b′

The obtained Sub 1-152-b (6.6 g, 24.9 mmol), Sub 2-20 (17.5 g, 49.8 mmol), Pd₂(dba)₃ (0.68 g, 0.75 mmol), P(t-Bu)₃ (50 wt % Sol.) (0.6 mL, 1.5 mmol), t-BuONa (7.18 g, 74.7 mmol) were added to anhydrous Toluene (150 mL) and reacted for 3 hours. After confirming the completion of the reaction, extraction was performed with CH₂Cl₂ and water, and the organic layer was dried over MgSO₄ and concentrated. The resulting compound was silica gel column and recrystallized to give a product 14.8 g (yield 60%).

(4) Synthesis Example of Sub 1-152-c

Sub 1″-152 (8.97 g, 14.9 mmol), n-BuLi (6 mL), Sub 1-152-b′ (14.8 g, 14.9 mmol) obtained in the above synthesis was used to obtain a product 14.0 g (62% yield) using the synthesis method of Sub 1-1-c.

(5) Synthesis Example of Sub 1-152

Sub 1-152-c (14 g, 9.3 mmol) obtained in the above synthesis, acetic acid (23 mL), and concentrated hydrochloric acid (3.8 mL) were used to obtain 8.7 g (63% yield) of the product using the synthesis method of Sub 1-1.

Meanwhile, the compound belonging to Sub 1 may be the following compound, but is not limited thereto, and Table 1 shows FD-MS (Field Desorption-Mass Spectrometry) values of the compound belonging to Sub 1.

TABLE 1 compound FD-MS compound FD-MS Sub1-1 m/z = 366.08(C₂₅H₁₅ClO = 366.84) Sub1-2 m/z = 366.08(C₂₅H₁₅ClO = 366.84) Sub1-3 m/z = 366.08(C₂₅H₁₅ClO = 366.84) Sub1-4 m/z = 366.08(C₂₅H₁₅ClO = 366.84) Sub1-5 m/z = 366.08(C₂₅H₁₅ClO = 366.84) Sub1-6 m/z = 366.08(C₂₅H₁₅ClO = 366.84) Sub1-7 m/z = 366.08(C₂₅H₁₅ClO = 366.84) Sub1-8 m/z = 366.08(C₂₅H₁₅ClO = 366.84) Sub1-9 m/z = 382.06(C₂₅H₁₅ClS = 382.91) Sub1-10 m/z = 382.06(C₂₅H₁₅ClS = 382.91) Sub1-11 m/z = 382.06(C₂₅H₁₅ClS = 382.91) Sub1-12 m/z = 382.06(C₂₅H₁₅ClS = 382.91) Sub1-13 m/z = 382.06(C₂₅H₁₅ClS = 382.91) Sub1-14 m/z = 382.06(C₂₅H₁₅ClS = 382.91) Sub1-15 m/z = 382.06(C₂₅H₁₅ClS = 382.91) Sub1-16 m/z = 382.06(C₂₅H₁₅ClS = 382.91) Sub1-17 m/z = 432.07(C₂₉H₁₇ClS = 432.97) Sub1-18 m/z = 432.07(C₂₉H₁₇ClS = 432.97) Sub1-19 m/z = 432.07(C₂₉H₁₇ClS = 432.97) Sub1-20 m/z = 432.07(C₂₉H₁₇ClS = 432.97) Sub1-21 m/z = 442.11(C₃₁H₁₉ClO = 442.94) Sub1-22 m/z = 408.07(C₂₇H₁₇ClS = 408.94) Sub1-23 m/z = 442.11(C₃₁H₁₉ClO = 442.94) Sub1-24 m/z = 508.11(C₃₅H₂₁ClS = 509.06) Sub1-25 m/z = 574.15(C₄₀H₂₇ClS = 575.17) Sub1-26 m/z = 442.11(C₃₁H₁₉ClO = 442.94) Sub1-27 m/z = 442.11(C₃₁H₁₉ClO = 442.94) Sub1-28 m/z = 532.12(C₃₇H₂₁ClO₂ = 533.02) Sub1-29 m/z = 443.11(C₃₀H₁₈ClNO = 443.93) Sub1-30 m/z = 416.10(C₂₉H₁₇ClO = 416.90) Sub1-31 m/z = 699.20(C₄₉H₃₀ClNO₂ = 700.23) Sub1-32 m/z = 699.20(C₄₉H₃₀ClNO₂ = 700.23) Sub1-33 m/z = 825.24(C₅₉H₃₆ClNO₂ = 826.39) Sub1-34 m/z = 941.31(C₆₈H₄₄ClNO₂ = 942.56) Sub1-35 m/z = 623.17(C₄₃H₂₆ClNO₂ = 624.14) Sub1-36 m/z = 825.24(C₅₉H₃₆ClNO₂ = 826.39) Sub1-37 m/z = 699.20(C₄₉H₃₀ClNO₂ = 700.23) Sub1-38 m/z = 715.17(C₄₉H₃₀ClNOS = 716.3) Sub1-39 m/z = 805.18(C₅₅H₃₂ClNO₂S = 806.38) Sub1-40 m/z = 749.21(C₃₃H₃₂ClNO₂ = 750.29) Sub1-41 m/z = 892.29(C₆₃H₄₁ClN₂O₂ = 893.48) Sub1-42 m/z = 623.17(C₄₃H₂₆ClNO₂ = 624.14) Sub1-43 m/z = 841.27(C₆₀H₄₀ClNO₂ = 842.44) Sub1-44 m/z = 805.18(C₅₅H₃₂ClNO₂S = 806.38) Sub1-45 m/z = 775.23(C₅₅H₃₄ClNO₂ = 776.33) Sub1-46 m/z = 815.26(C₅₈H₃₈ClNO₂ = 816.40) Sub1-47 m/z = 623.17(C₄₃H₂₆ClNO₂ = 624.14) Sub1-48 m/z = 699.20(C₄₉H₃₀ClNO₂ = 700.23) Sub1-49 m/z = 936.22(C₆₃H₃₇ClN₂O₃S = 937.51) Sub1-50 m/z = 855.20(C₅₉H₃₄ClNO₂S = 856.44) Sub1-51 m/z = 699.20(C₄₉H₃₀ClNO₂ = 700.23) Sub1-52 m/z = 699.20(C₄₉H₃₀ClNO₂ = 700.23) Sub1-53 m/z = 897.25(C₆₂H₄₀ClNO₂S = 898.52) Sub1-54 m/z = 957.28(C₆₈H₄₄ClNOS = 958.62) Sub1-55 m/z = 739.19(C₅₁H₃₀ClNO₃ = 740.26) Sub1-56 m/z = 917.25(C₆₅H₄₀ClNOS = 918.55) Sub1-57 m/z = 791.20(C₅₅H₃₄ClNOS = 792.39) Sub1-58 m/z = 699.20(C₄₉H₃₀ClNO₂ = 700.23) Sub1-59 m/z = 897.19(C₆₁H₃₆ClNOS₂ = 898.54) Sub1-60 m/z = 749.21(C₅₃H₃₂ClNO₂ = 750.29) Sub1-61 m/z = 805.18(C₅₅H₃₂ClNO₂S = 806.38) Sub1-62 m/z = 755.17(C₅₁H₃₀ClNO₂S = 756.32) Sub1-63 m/z = 1088.32(C₇₆H₄₉ClN₂O₂S = 1089.75) Sub1-64 m/z = 699.20(C₄₉H₃₀ClNO₂ = 700.23) Sub1-65 m/z = 891.29(C₆₄H₄₂ClNO₂ = 892.50) Sub1-66 m/z = 639.14(C₄₃H₂₆ClNOS = 640.20) Sub1-67 m/z = 715.17(C₄₉H₃₀ClNOS = 716.30) Sub1-68 m/z = 715.17(C₄₉H₃₀ClNOS = 716.3) Sub1-69 m/z = 841.22(C₅₉H₃₆ClNOS = 842.45) Sub1-70 m/z = 957.28(C₆₈H₄₄ClNOS = 958.62) Sub1-71 m/z = 639.14(C₄₃H₂₆ClNOS = 640.20) Sub1-72 m/z = 917.25(C₆₅H₄₀ClNOS = 918.55) Sub1-73 m/z = 841.22(C₅₉H₃₆ClNOS = 842.45) Sub1-74 m/z = 731.15(C₄₉H₃₀ClNS₂ = 732.36) Sub1-75 m/z = 821.16(C₅₅H₃₂ClNOS₂ = 822.44) Sub1-76 m/z = 765.19(C₅₃H₃₂ClNOS = 766.36) Sub1-77 m/z = 908.26(C₆₃H₄₁ClN₂OS = 909.54) Sub1-78 m/z = 873.23(C₆₀H₄₀ClNS₂ = 874.56) Sub1-79 m/z = 731.15(C₄₉H₃₀ClNS₂ = 732.36) Sub1-80 m/z = 821.16(C₅₅H₃₂ClNOS₂ = 822.44) Sub1-81 m/z = 715.17(C₄₉H₃₀ClNOS = 716.30) Sub1-82 m/z = 791.20(C₅₅H₃₄ClNOS = 792.39) Sub1-83 m/z = 639.14(C₄₃H₂₆ClNOS = 640.20) Sub1-84 m/z = 847.21(C₅₈H₃₈ClNS₂ = 848.52) Sub1-85 m/z = 936.22(C₆₃H₃₇ClN₂O₃S = 937.51) Sub1-86 m/z = 731.15(C₄₉H₃₀ClNS₂ = 732.36) Sub1-87 m/z = 731.15(C₄₉H₃₀ClNS₂ = 732.36) Sub1-88 m/z = 855.20(C₅₉H₃₄ClNO₂S = 856.44) Sub1-89 m/z = 715.17(C₄₉H₃₀ClNOS = 716.30) Sub1-90 m/z = 947.26(C₆₆H₄₂ClNO₂S = 948.58) Sub1-91 m/z = 755.17(C₅₁H₃₀ClNO₂S = 756.32) Sub1-92 m/z = 1007.30(C₇₂H₄₆ClNOS = 1008.68) Sub1-93 m/z = 791.20(C₅₅H₃₄ClNOS = 792.39) Sub1-94 m/z = 917.25(C₆₅H₄₀ClNOS = 918.55) Sub1-95 m/z = 956.26(C₆₇H₄₁ClN₂OS = 957.59) Sub1-96 m/z = 972.24(C₆₇H₄₁ClN₂S₂ = 973.65) Sub1-97 m/z = 765.19(C₅₃H₃₂ClNOS = 766.36) Sub1-98 m/z = 821.16(C₅₅H₃₂ClNOS₂ = 822.44) Sub1-99 m/z = 771.15(C₅₁H₃₀ClNOS₂ = 772.38) Sub1-100 m/z = 1104.30(C₇₆H₄₉ClN₂OS₂ = 1105.81) Sub1-101 m/z = 907.27(C₆₄H₄₂ClNOS = 908.56) Sub1-102 m/z = 715.17(C₄₉H₃₀ClNOS = 716.03) Sub1-103 m/z = 1032.31(C₇₃H₄₅ClN₂O₃ = 1033.62) Sub1-104 m/z = 1048.29(C₇₃H₄₅ClN₂O₂S = 1049.69) Sub1-105 m/z = 1048.29(C₇₃H₄₅ClN₂O₂S = 1049.69) Sub1-106 m/z = 1154.28(C₇₉H₄₇ClN₂O₂S₂ = 1155.83) Sub1-107 m/z = 1264.35(C₈₉H₅₃ClN₂O₃S = 1265.92) Sub1-108 m/z = 1174.34(C₈₃H₅₁ClN₂O₂S = 1175.84) Sub1-109 m/z = 1406.42(C₁₀₀H₆₃ClN₂O₃S = 1408.13) Sub1-110 m/z = 1274.39(C₉₁H₅₅ClN₂O₄ = 1275.90) Sub1-111 m/z = 1240.38(C₈₈H₅₇ClN₂O₂S = 1241.95) Sub1-112 m/z = 1048.29(C₇₃H₄₅ClN₂O₂S = 1049.69) Sub1-113 m/z = 1174.34(C₈₃H₅₁ClN₂O₂S = 1175.84) Sub1-114 m/z = 1190.31(C₈₃H₅₁ClN₂OS₂ = 1191.90) Sub1-115 m/z = 1138.30(C₇₉H₄₇ClN₂O₃S = 1139.77) Sub1-116 m/z = 1154.28(C₇₉H₄₇ClN₂O₂S₂ = 1155.83) Sub1-117 m/z = 1048.29(C₇₃H₄₅ClN₂O₂S = 1049.69) Sub1-118 m/z = 1270.34(C₈₈H₅₅ClN₂O₂S₂ = 1271.99) Sub1-119 m/z = 1188.32(C₈₃H₄₉ClN₂O₃S = 1189.83) Sub1-120 m/z = 1214.37(C₈₆H₅₅ClN₂O₂S = 1215.91) Sub1-121 m/z = 1141.29(C₇₈H₄₈ClN₃OS₂ = 1142.83) Sub1-122 m/z = 1140.30(C₇₉H₄₉ClN₂OS₂ = 1141.84) Sub1-123 m/z = 1141.29(C₇₈H₄₈ClN₃OS₂ = 1142.83) Sub1-124 m/z = 1250.37(C₈₉H₅₅ClN₂O₂S = 1251.94) Sub1-125 m/z = 1124.32(C₇₉H₄₉ClN₂O₂S = 1125.78) Sub1-126 m/z = 1266.34(C₈₉H₅₅ClN₂OS₂ = 1268.00) Sub1-127 m/z = 1229.32(C₈₅H₅₂ClN₃OS₂ = 1230.94) Sub1-128 m/z = 1229.32(C₈₅H₅₂ClN₃OS₂ = 1230.94) Sub1-129 m/z = 1048.29(C₇₃H₄₅ClN₂O₂S = 1049.69) Sub1-130 m/z = 1114.28(C₇₇H₄₇ClN₂OS₂ = 1115.81) Sub1-131 m/z = 1170.25(C₇₉H₄₇ClN₂OS₃ = 1171.89) Sub1-132 m/z = 1204.29(C₈₃H₄₉ClN₂O₂S₂ = 1205.89) Sub1-133 m/z = 1477.44(C₁₀₃H₆₈ClN₃O₂S₂ = 1479.27) Sub1-134 m/z = 1154.28(C₇₉H₄₇ClN₂O₂S₂ = 1155.83) Sub1-135 m/z = 1471.49(C₁₀₅H₇₀ClN₃O₂S = 1473.24) Sub1-136 m/z = 1064.27(C₇₃H₄₃ClN₂OS₂ = 1065.75) Sub1-137 m/z = 1256.36(C₈₈H₅₇ClN₂OS₂ = 1258.01) Sub1-138 m/z = 1240.38(C₈₈H₅₇ClN₂O₂S = 1241.95) Sub1-139 m/z = 1140.30(C₇₉H₄₉ClN₂OS₂ = 1141.84) Sub1-140 m/z = 1140.30(C₇₉H₄₉ClN₂OS₂ = 1141.84) Sub1-141 m/z = 1124.32(C₇₉H₄₉ClN₂O₂S = 1125.78) Sub1-142 m/z = 1170.25(C₇₉H₄₇ClN₂OS₃ = 1171.89) Sub1-143 m/z = 1280.32(C₈₉H₅₃ClN₂O₂S₂ = 1281.99) Sub1-144 m/z = 1190.31(C₈₃H₅₁ClN₂OS₂ = 1191.90) Sub1-145 m/z = 1422.40(C₁₀₀H₆₃ClN₂O₂S₂ = 1424.19) Sub1-146 m/z = 1290.36(C₉₁H₅₅ClN₂O₃S = 1291.96) Sub1-147 m/z = 1256.36(C₈₈H₅₇ClN₂OS₂ = 1258.01) Sub1-148 m/z = 1256.31(C₈₇H₅₃ClN₂S₃ = 1258.03) Sub1-149 m/z = 1130.26(C₇₇H₄₇ClN₂S₃ = 1131.87) Sub1-150 m/z = 1206.29(C₈₃H₅₁ClN₂S₃ = 1207.97) Sub1-151 m/z = 1236.39(C₈₃H₆₂Cl₂N₂O₃S = 1238.38) Sub1-152 m/z = 1493.57(C₁₀₃H₈₄ClN₃O₂S₂ = 1495.39) Sub1-153 m/z = 1599.56(C₁₀₉H₈₆ClN₃O₂S₃ = 1601.54) Sub1-154 m/z = 1214.24(C₈₁H₄₈Cl₂N₂S₃ = 1216.37) Sub1-155 m/z = 1082.25(C₇₃H₄₄Cl₂N₂O₂S = 1084.13) Sub1-156 m/z = 508.11(C₃₅H₂₁ClS = 509.06) Sub1-157 m/z = 442.11(C₃₁H₁₉ClO = 442.94) Sub1-158 m/z = 1252.36(C₈₃H₆₂Cl₂N₂O₂S₂ = 1254.44) Sub1-159 m/z = 1509.55(C₁₀₃H₈₄ClN₃OS₃ = 1511.46) Sub1-160 m/z = 1615.53(C₁₀₉H₈₆ClN₃OS₄ = 1617.60) Sub1-161 m/z = 391.08(C₂₆H₁₄ClNO = 391.85) Sub1-162 m/z = 459.08(C₃₀H₁₈ClNS = 459.99) Sub1-163 m/z = 442.11(C₃₁H₁₉ClO = 442.94) Sub1-164 m/z = 442.11(C₃₁H₁₉ClO = 442.94) Sub1-165 m/z = 442.11(C₃₁H₁₉ClO = 442.94) Sub1-166 m/z = 458.09(C₃₁H₁₉ClS = 459.00) Sub1-167 m/z = 458.09(C₃₁H₁₉ClS = 459.00) Sub1-168 m/z = 458.09(C₃₁H₁₉ClS = 459.00) Sub1-169 m/z = 391.08(C₂₆H₁₄ClNO = 391.85) Sub1-170 m/z = 408.07(C₂₇H₁₇ClS = 408.94) Sub1-171 m/z = 416.10(C₂₉H₁₇ClO = 416.90) Sub1-172 m/z = 460.08(C₂₉H₁₇ClN₂S = 460.98) Sub1-173 m/z = 466.11(C₃₃H₁₉ClO = 466.96) Sub1-174 m/z = 458.09(C₃₁H₁₉ClS = 459) Sub1-175 m/z = 458.09(C₃₁H₁₉ClS = 459) Sub1-176 m/z = 474.08(C₃₁H₁₉ClOS = 475) Sub1-177 m/z = 422.14(C₂₉H₂₃C₁₀ = 422.95)

II. Synthesis of Sub 2

Sub 2 of Reaction Scheme 1 may be synthesized by the reaction route of Scheme 3 below, but is not limited thereto. Sub 3 and Sub 4 are also included in Sub 2.

In Reaction Scheme 3,

Y, Ar¹′, Ar²′, R^(1′), L¹′, e′ and f′ are the same as defined above, Hal¹′ is Br or Cl.

Synthesis examples of specific compounds belonging to Sub 2 are as follows.

1. Synthesis Example of Sub 2-8

(1) Synthesis Example of Sub 2-8-a

4-bromo-2-chlorophenol (15 g, 73.5 mmole) was dissolved in a round bottom flask with DMF (400 mL) and iodobenzene (16.8 g, 80.9 mmol), K₂CO₃ (20.3 g 147.1 mmol), Cu (2.3 g, 36.8 mmol), Dibenzo-18-crown-6 (1.6 g, 4.4 mmole) were added and stirred at 120° C. When the reaction was completed, the solvent was removed, extracted with CH₂Cl₂ and water, the organic layer was dried over MgSO₄, concentrated, and the resulting compound was silica gel column to obtain 16.5 g (yield 79%) of the product.

(2) Synthesis Example of Sub 2-8-b

Acetic acid (400 mL) was added to 4-bromo-2-chloro-1-phenoxybenzene (16 g, 56.4 mmol)0∥ Pd(OAc)₂ (0.63 g, 2.8 mol), K₂CO₃ (7.8 g, 56.4 mol) and stirred at 120° C. for 48 hours. When the reaction was completed, the solvent was removed, extracted with Ethyl Acetate and water, the organic layer was dried over MgSO₄, concentrated, and the resulting compound was silica gel column to obtain 6.7 g (yield 42%) of the product.

(3) Synthesis Example of Sub 2-8-c

Sub 2-8-b (6.7 g, 23.8 mmol) obtained in the above synthesis, phenylboronic acid (2.9 g, 23.8 mmol) was added, dissolved in THF (100 mL), and Pd(PPh₃)₄ (1.4 g, 1.2 mmol) and K₂CO₃ (19.9 g, 71.4 mmol) were added, respectively, and then refluxed for 24 hours. When the reaction was completed, the solvent was removed, extracted with CH₂Cl₂ and water, the organic layer was dried over MgSO₄, concentrated, and the resulting compound was silica gel column to obtain 4.98 g (yield 75%) of the product.

(4) Synthesis Example of Sub 2-8

After dissolving Sub 2-8-c (4.98 g, 17.9 mmol) obtained in the above synthesis with Toluene (100 ml) in a round bottom flask, Aniline (1.83 g, 19.7 mmol), Pd₂(dba)₃ (0.49 g, 0.54 mmol), P(t-Bu)₃ (50 wt % Sol.) (0.43 mL, 1.07 mmol), NaOt-Bu (5.2 g, 53.6 mmol) were added and stirred at 80° C. When the reaction was completed, the solvent was removed, extracted with CH₂Cl₂ and water, the organic layer was dried over MgSO₄, concentrated, and the resulting compound was silica gel column to obtain 4.8 g (yield 80%) of the product.

2. Synthesis Example of Sub 2-43

(1) Synthesis Example of Sub 2-43-a

(2-(methylthio)phenyl)boronic acid (30 g, 137.6 mmol) was dissolved in a round bottom flask with THF (300 mL) and 4-bromo-2-chloroiodobenzene (43.7 g, 137.6 mmol), Pd(PPh₃)₄ (4.8 g, 4.1 mmol), K₂CO₃ (57 g, 412.7 mmol), and water (100 mL) were added and stirred at 80° C. When the reaction was completed, the solvent was removed, extracted with CH₂Cl₂ and water, the organic layer was dried over MgSO₄, concentrated, and the resulting compound was silica gel column to obtain 37.5 g (yield 75%) of the product.

(2) Synthesis Example of Sub 2-43-a′

Sub 2-43-a (37 g, 101.7 mmol) obtained in the above synthesis was dissolved in AcOH (300 mL) in a round bottom flask, H₂O₂ (8.7 mL, 101.7 mmol) was added and stirred at room temperature. When the reaction was completed, the solvent was removed, neutralized with 1M NaOH, extracted with Ethyl acetate, and recrystallized to obtain 35.5 g (92% yield) of the product.

(3) Synthesis Example of Sub 2-43-b

Sub 2-43-a′ (35 g, 92.2 mmol) obtained in the above synthesis was added to 300 g of Trifluloromethanesulfonic acid and stirred at 65° C. When the reaction was completed, pyridine was added and refluxed for 30 minutes, and the resulting compound was recrystallized in a silica gel column to obtain 26 g (yield 81%) of the product.

(4) Synthesis Example of Sub 2-43-c

Sub 2-43-b (26 g, 74.8 mmol) obtained in the above synthesis, phenylboronic acid (9.12 g, 74.8 mmol), Pd(PPh₃)₄ (4.32 g, 3.7 mmol), K₂CO₃ (62.54 g, 224.4 mmol) was added to THF (180 mL), and by using the synthesis method of Sub 2-8-c, the product 20.1 g (78% yield) was obtained.

(5) Synthesis Example of Sub 2-43

Sub 2-43-c (20.1 g, 58.3 mmol) obtained in the above synthesis was dissolved in a round bottom flask with Toluene (400 ml), and Aniline (6 g, 64.1 mmol), Pd₂(dba)₃ (1.6 g, 1.75 mmol), P(t-Bu)₃ (50 wt % Sol.) (1.42 mL, 3.5 mmol), NaOt-Bu (16.8 g, 174.85 mmol) were added, and product 23.4 g (yield 79%) was obtained using the synthesis method of Sub 2-8.

Sub 5 of Scheme 1-1 may be synthesized by the reaction route of Scheme 3-1, but is not limited thereto.

Hal³′ in Scheme 3-1 is Cl or Br.

1. Synthesis Example of Sub 5-2

Sub 1-1 (13.5 g, 36.8 mmol) was added in a round bottom flask and dissolved in Toluene (270 mL), and [1,1′-biphenyl]-2-amine (6.23 g, 36.8 mmol), Pd₂(dba)₃ (1.68 g, 1.84 mmol), P(t-Bu)₃ (50 wt % Sol.) (1.49 mL, 3.68 mmol), NaOt-Bu (10.61 g, 110 mmol) were added and stirred at 80° C. After the reaction was completed, the reaction mixture was extracted with CH₂Cl₂ and water. The organic layer was dried over MgSO₄ and concentrated. The resulting compound was separated by silica gel column chromatography and recrystallized to obtain 14.9 g of the product. (yield:81%).

2. Synthesis Example of Sub 5-12

Sub 1-9 (12.2 g, 31.9 mmol) was added in a round bottom flask and dissolved in Toluene (244 mL), 7-phenylnaphthalen-2-amine (6.99 g, 31.9 mmol), Pd₂(dba)₃ (1.46 g, 1.59 mmol), P(t-Bu)₃ (50 wt % Sol.) (1.29 mL, 3.19 mmol), NaOt-Bu (9.19 g, 95.6 mmol) were added thereto, and 15.0 g of a product (yield 83%) was obtained using the synthesis method of Sub 5-2.

3. Synthesis Example of Sub 5-19

Sub 1-14 (10.5 g, 27.4 mmol) was added in a round bottom flask and dissolved in Toluene (210 mL), naphthalen-2-amine (3.93 g, 27.4 mmol), Pd₂(dba)₃ (1.26 g, 1.37 mmol), P(t-Bu)₃ (50 wt % Sol.) (1.11 mL, 2.74 mmol), NaOt-Bu (7.91 g, 82.3 mmol) were added thereto, and 10.1 g of a product (yield 75%) was obtained using the synthesis method of Sub 5-2.

Meanwhile, the compound belonging to Sub 2 and Sub 5 may be the following compound, but it is not limited thereto. Sub 3 and Sub 4 are also compounds belonging to Sub 2, and Table 2 below shows the FD-MS values of the compounds belonging to Sub 2 and Sub 5.

TABLE 2 compound FD-MS compound FD-MS Sub2-1 m/z = 335.13(C₂₄H₁₇NO = 335.41) Sub2-2 m/z = 427.19(C₃₁H₂₅NO = 427.55) Sub2-3 m/z = 561.21(C₄₂H₂₇NO = 561.68) Sub2-4 m/z = 461.18(C₃₄H₂₃NO = 461.56) Sub2-5 m/z = 461.18(C₃₄H₂₃NO = 461.56) Sub2-6 m/z = 435.16(C₂₄H₁₇NO = 435.53) Sub2-7 m/z = 335.13(C₂₄H₁₇NO = 335.41) Sub2-8 m/z = 335.13(C₃₂H₂₁NO = 335.41) Sub2-9 m/z = 527.22(C₃₉H₂₉NO = 527.67) Sub2-10 m/z = 511.19(C₃₈H₂₅NO = 511.62) Sub2-11 m/z = 487.19(C₃₆H₂₅NO = 487.60) Sub2-12 m/z = 537.21(C₄₀H₂₇NO = 537.66) Sub2-13 m/z = 435.16(C₃₂H₂₁NO = 435.53) Sub2-14 m/z = 336.13(C₂₃H₁₆N₂O = 336.39) Sub2-15 m/z = 452.15(C₃₁H₂₀N₂O₂ = 452.51) Sub2-16 m/z = 500.19(C₃₆H₂₄N₂O = 500.60) Sub2-17 m/z = 465.20(C₃₄H₁₉D₄NO = 465.59) Sub2-18 m/z = 482.11(C₃₁H₁₈N₂O₂S = 482.56) Sub2-19 m/z = 567.17(C₄₀H₂₅NOS = 567.71) Sub2-20 m/z = 351.11(C₂₄H₁₇NS = 351.47) Sub2-21 m/z = 475.14(C₃₄H₂₁NS = 475.61) Sub2-22 m/z = 477.16(C₃₄H₂₃NS = 477.63) Sub2-23 m/z = 577.19(C₄₂H₂₇NS = 577.75) Sub2-24 m/z = 477.16(C₃₄H₂₃NS = 477.63) Sub2-25 m/z = 467.17(C₃₃H₂₅NS = 467.63) Sub2-26 m/z = 427.14(C₃₀H₂₁NS = 427.57) Sub2-27 m/z = 441.12(C₃₀H₁₉NOS = 441.55) Sub2-28 m/z = 427.14(C₃₀H₂₁NS = 427.57) Sub2-29 m/z = 457.10(C₃₀H₁₉NS₂ = 457.61) Sub2-30 m/z = 527.17(C₃₈H₂₅NS = 527.69) Sub2-31 m/z = 517.15(C₃₆H₂₃NOS = 517.65) Sub2-32 m/z = 352.10(C₂₃H₁₆N₂S = 352.46) Sub2-33 m/z = 451.14(C₃₂H₂₁NS = 451.59) Sub2-34 m/z = 553.19(C₄₀H₂₇NS = 553.72) Sub2-35 m/z = 503.17(C₃₆H₂₅NS = 503.66) Sub2-36 m/z = 451.14(C₃₂H₂₁NS = 451.59) Sub2-37 m/z = 592.20(C₄₂H₂₈N₂S = 592.76) Sub2-38 m/z = 583.14(C₄₀H₂₅NS₂ = 583.77) Sub2-39 m/z = 385.15(C₂₈H₁₉NO = 385.47) Sub2-40 m/z = 352.10(C₂₃H₁₆N₂S = 352.46) Sub2-41 m/z = 401.12(C₂₈H₁₉NS = 401.53) Sub2-42 m/z = 477.16(C₃₄H₂₃NS = 477.63) Sub2-43 m/z = 507.11(C₃₄H₂₁NS₂ = 507.67) Sub2-44 m/z = 553.19(C₄₀H₂₇NS = 553.72) Sub2-45 m/z = 527.17(C₃₈H₂₅NS = 527.69) Sub2-46 m/z = 517.15(C₃₆H₂₃NOS = 517.65) Sub2-47 m/z = 498.09(C₃₁H₁₈N₂OS₂ = 498.62) Sub2-48 m/z = 427.14(C₃₀H₂₁NS = 427.57) Sub2-49 m/z = 468.13(C₃₁H₂₀N₂OS = 468.57) Sub2-50 m/z = 385.15(C₂₈H₁₉NO = 385.47) Sub2-51 m/z = 441.12(C₃₀H₁₉NOS = 441.55) Sub2-52 m/z = 367.14(C₂₅H₂₁NS = 367.51) Sub2-53 m/z = 577.24(C₄₃H₃₁NO = 577.73) Sub2-54 m/z = 351.16(C₂₅H₂₁NO = 351.45) Sub2-55 m/z = 435.16(C₃₂H₂₁NO = 435.53) Sub2-56 m/z = 451.19(C₃₃H₂₅NO = 451.57) Sub2-57 m/z = 427.19(C₃₁H₂₅NO = 427.55) Sub2-58 m/z = 441.12(C₃₀H₁₉NOS = 441.55) Sub2-59 m/z = 477.21(C₃₅H₂₇NO = 477.61) Sub2-60 m/z = 528.22(C₃₈H₂₈N₂O = 528.66) Sub2-61 m/z = 375.13(C₂₆H₁₇NO₂ = 375.43) Sub2-62 m/z = 609.25(C₄₄H₃₅NS = 609.83) Sub2-63 m/z = 533.18(C₃₇H₂₇NOS = 533.69) Sub2-64 m/z = 507.17(C₃₅H₂₅NOS = 507.65) Sub2-65 m/z = 572.16(C₃₈H₂₄N₂O₂S = 572.68) Sub2-66 m/z = 391.10(C₂₅H₁₇NOS = 391.49) Sub2-67 m/z = 724.25(C₅₁H₃₆N₂OS = 724.92) Sub2-68 m/z = 527.22(C₃₉H₂₉NO = 527.67) Sub2-69 m/z = 441.12(C₃₀H₁₉NOS = 441.55) Sub2-70 m/z = 493.19(C₃₅H₂₇NS = 493.67) Sub2-71 m/z = 467.17(C₃₃H₂₅NS = 467.63) Sub2-72 m/z = 556.18(C₃₈H₂₄N₂O₃ = 556.62) Sub2-73 m/z = 475.16(C₃₄H₂₁NO₂ = 475.55) Sub2-74 m/z = 567.22(C₄₁H₂₉NO₂ = 567.69) Sub2-75 m/z = 627.26(C₄₇H₃₃NO = 627.79) Sub2-76 m/z = 527.22(C₃₉H₂₉NO = 527.67) Sub2-77 m/z = 335.13(C₂₄H₁₇NO = 335.41) Sub2-78 m/z = 467.17(C₃₃H₂₅NS = 467.63) Sub2-79 m/z = 501.17(C₃₆H₂₃NO₂ = 501.59) Sub2-80 m/z = 351.11(C₂₄H₁₇NS = 351.47) Sub2-81 m/z = 351.11(C₂₄H₁₇NS = 351.47) Sub2-82 m/z = 516.17(C₃₆H₂₄N₂S = 516.66) Sub2-83 m/z = 708.31(C₅₂H₄₀N₂O = 708.91) Sub2-84 m/z = 401.12(C₂₈H₁₉NS = 401.53) Sub2-85 m/z = 401.12(C₂₈H₁₉NS = 401.53) Sub2-86 m/z = 351.11(C₂₄H₁₇NS = 351.47) Sub2-87 m/z = 518.18(C₃₆H₂₆N₂S = 518.68) Sub2-88 m/z = 427.14(C₃₀H₂₁NS = 427.57) Sub2-89 m/z = 461.18(C₃₄H₂₃NO = 461.56) Sub2-90 m/z = 461.18(C₃₄H₂₃NO = 461.56) Sub2-91 m/z = 335.13(C₂₄H₁₇NO = 335.41) Sub2-92 m/z = 561.21(C₄₂H₂₇NO = 561.68) Sub2-93 m/z = 461.18(C₃₄H₂₃NO = 461.56) Sub2-94 m/z = 353.12(C₂₄H₁₆FNO = 353.40) Sub2-95 m/z = 391.19(C₂₈H₂₅NO = 391.51) Sub2-96 m/z = 259.10(C₁₈H₁₃NO = 259.31) Sub2-97 m/z = 275.08(C₁₈H₁₃NS = 275.37) Sub3-1 m/z = 375.16(C₂₇H₂₁NO = 375.47) Sub3-2 m/z = 375.16(C₂₇H₂₁NO = 375.47) Sub3-3 m/z = 375.16(C₂₇H₂₁NO = 375.47) Sub3-4 m/z = 391.14(C₂₇H₂₁NS = 391.53) Sub3-5 m/z = 499.19(C₃₇H₂₅NO = 499.61) Sub3-6 m/z = 499.19(C₃₇H₂₅NO = 499.61) Sub3-7 m/z = 499.19(C₃₇H₂₅NO = 499.61) Sub3-8 m/z = 499.19(C₃₇H₂₅NO = 499.61) Sub3-9 m/z = 515.17(C₃₇H₂₅NS = 515.67) Sub3-10 m/z = 497.18(C₃₇H₂₃NO = 497.60) Sub3-11 m/z = 513.16(C₃₇H₂₃NS = 513.66) Sub3-12 m/z = 451.19(C₃₃H₂₅NO = 451.57) Sub3-13 m/z = 467.17(C₃₃H₂₅NS = 467.63) Sub3-14 m/z = 451.19(C₃₃H₂₅NO = 451.57) Sub3-15 m/z = 467.17(C₃₃H₂₅NS = 467.63) Sub3-16 m/z = 451.19(C₃₃H₂₅NO = 451.57) Sub3-17 m/z = 467.17(C₃₃H₂₅NS = 467.63) Sub3-18 m/z = 451.19(C₃₃H₂₅NO = 451.57) Sub3-19 m/z = 451.19(C₃₃H₂₅NO = 451.57) Sub3-20 m/z = 451.19(C₃₃H₂₅NO = 451.57) Sub3-21 m/z = 451.19(C₃₃H₂₅NO = 451.57) Sub3-22 m/z = 467.17(C₃₃H₂₅NS = 467.63) Sub3-23 m/z = 467.17(C₃₃H₂₅NS = 467.63) Sub3-24 m/z = 467.17(C₃₃H₂₅NS = 467.63) Sub3-25 m/z = 501.21(C₃₇H₂₇NO = 501.63) Sub3-26 m/z = 517.19(C₃₇H₂₇NS = 517.69) Sub3-27 m/z = 501.21(C₃₇H₂₇NO = 501.63) Sub3-28 m/z = 517.19(C₃₇H₂₇NS = 517.69) Sub3-29 m/z = 501.21(C₃₇H₂₇NO = 501.63) Sub3-30 m/z = 517.19(C₃₇H₂₇NS = 517.69) Sub3-31 m/z = 452.19(C₃₂H₂₄N₂O = 452.56) Sub3-32 m/z = 583.23(C₄₂H₃₃NS = 583.79) Sub3-33 m/z = 525.21(C₃₉H₂₇NO = 525.65) Sub3-34 m/z = 519.20(C₃₇H₂₁D₄NS = 519.70) Sub3-35 m/z = 527.22(C₃₉H₂₉NO = 527.67) Sub3-36 m/z = 543.20(C₃₉H₂₉NS = 543.73) Sub3-37 m/z = 527.22(C₃₉H₂₉NO = 527.67) Sub3-38 m/z = 543.20(C₃₉H₂₉NS = 543.73) Sub3-39 m/z = 543.20(C₃₉H₂₉NS = 543.73) Sub3-40 m/z = 527.22(C₃₉H₂₉NO = 527.67) Sub3-41 m/z = 527.22(C₃₉H₂₉NO = 527.67) Sub3-42 m/z = 527.22(C₃₉H₂₉NO = 527.67) Sub3-43 m/z = 543.20(C₃₉H₂₉NS = 543.73) Sub3-44 m/z = 543.20(C₃₉H₂₉NS = 543.73) Sub3-45 m/z = 452.19(C₃₂H₂₄N₂O = 452.56) Sub3-46 m/z = 441.16(C₃₁H₂₃NS = 441.59) Sub3-47 m/z = 441.16(C₃₁H₂₃NS = 441.59) Sub3-48 m/z = 425.18(C₃₁H₂₃NO = 425.53) Sub3-49 m/z = 425.18(C₃₁H₂₃NO = 425.53) Sub3-50 m/z = 467.17(C₃₃H₂₅NS = 467.63) Sub3-51 m/z = 577.24(C₄₃H₃₁NO = 577.73) Sub3-52 m/z = 573.21(C₄₃H₂₇NO = 573.70) Sub3-53 m/z = 497.18(C₃₇H₂₃NO = 497.60) Sub3-54 m/z = 497.18(C₃₇H₂₃NO = 497.60) Sub3-55 m/z = 513.16(C₃₇H₂₃NS = 513.66) Sub3-56 m/z = 441.16(C₃₁H₂₃NS = 441.59) Sub3-57 m/z = 549.21(C₄₁H₂₇NO = 549.67) Sub4-1 m/z = 513.17(C₃₇H₂₃NO₂ = 513.60) Sub4-2 m/z = 513.17(C₃₇H₂₃NO₂ = 513.60) Sub4-3 m/z = 513.17(C₃₇H₂₃NO₂ = 513.60) Sub4-4 m/z = 513.17(C₃₇H₂₃NO₂ = 513.60) Sub4-5 m/z = 579.17(C₄₁H₂₅NOS = 579.72) Sub4-6 m/z = 531.16(C₃₇H₂₂FNO₂ = 531.59) Sub4-7 m/z = 563.19(C₄₁H₂₅NO₂ = 563.66) Sub4-8 m/z = 665.24(C₄₉H₃₁NO₂ = 665.79) Sub4-9 m/z = 529.15(C₃₇H₂₃NOS = 529.66) Sub4-10 m/z = 529.15(C₃₇H₂₃NOS = 529.66) Sub4-11 m/z = 529.15(C₃₇H₂₃NOS = 529.66) Sub4-12 m/z = 529.15(C₃₇H₂₃NOS = 529.66) Sub4-13 m/z = 529.15(C₃₇H₂₃NOS = 529.66) Sub4-14 m/z = 529.15(C₃₇H₂₃NOS = 529.66) Sub4-15 m/z = 529.15(C₃₇H₂₃NOS = 529.66) Sub4-16 m/z = 529.15(C₃₇H₂₃NOS = 529.66) Sub4-17 m/z = 545.13(C₃₇H₂₃NS₂ = 545.72) Sub4-18 m/z = 589.20(C₄₃H₂₇NO₂ = 589.69) Sub4-19 m/z = 605.18(C₄₃H₂₇NOS = 605.76) Sub4-20 m/z = 605.18(C₄₃H₂₇NOS = 605.76) Sub4-21 m/z = 621.16(C₄₃H₂₇NS₂ = 621.82) Sub4-22 m/z = 655.20(C₄₇H₂₉NOS = 655.82) Sub4-23 m/z = 671.17(C₄₇H₂₉NS₂ = 671.88) Sub4-24 m/z = 606.18(C₄₂H₂₆N₂OS = 606.74) Sub4-25 m/z = 622.15(C₄₂H₂₆N₂S₂ = 622.80) Sub4-26 m/z = 589.20(C₄₃H₂₇NO₂ = 589.69) Sub4-27 m/z = 605.18(C₄₃H₂₇NOS = 605.76) Sub4-28 m/z = 589.20(C₄₃H₂₇NO₂ = 589.69) Sub4-29 m/z = 605.18(C₄₃H₂₇NOS = 605.76) Sub4-30 m/z = 605.18(C₄₃H₂₇NOS = 605.76) Sub4-31 m/z = 621.16(C₄₃H₂₇NS₂ = 621.82) Sub4-32 m/z = 563.19(C₄₁H₂₅NO₂ = 563.66) Sub4-33 m/z = 595.14(C₄₁H₂₅NS₂ = 595.78) Sub4-34 m/z = 579.17(C₄₁H₂₅NOS = 579.72) Sub4-35 m/z = 605.18(C₄₃H₂₇NOS = 605.76) Sub4-36 m/z = 671.17(C₄₇H₂₉NS₂ = 671.88) Sub4-37 m/z = 665.24(C₄₉H₃₁NO₂ = 665.79) Sub4-38 m/z = 549.15(C₃₇H₁₉D₄NS₂ = 549.74) Sub4-39 m/z = 665.24(C₄₉H₃₁NO₂ = 665.79) Sub4-40 m/z = 589.20(C₄₃H₂₇NO₂ = 589.69) Sub4-41 m/z = 671.17(C₄₇H₂₉NS₂ = 671.88) Sub4-42 m/z = 595.14(C₄₁H₂₅NS₂ = 595.78) Sub4-43 m/z = 595.14(C₄₁H₂₅NS₂ = 595.78) Sub4-44 m/z = 563.19(C₄₁H₂₅NO₂ = 563.66) Sub4-45 m/z = 589.2(C₄₃H₂₇NO₂= 589.69) Sub4-46 m/z = 589.2(C₄₃H₂₇NO₂ = 589.69) Sub4-47 m/z = 605.18(C₄₃H₂₇NOS = 605.76) Sub4-48 m/z = 623.17(C₄₃H₂₆FNOS = 623.75) Sub4-49 m/z = 610.21 (C₄₃H₂₂D₅NOS = 610.79) Sub4-50 m/z = 605.18(C₄₃H₂₇NOS = 605.76) Sub4-51 m/z = 605.18(C₄₃H₂₇NOS = 605.76) Sub4-52 m/z = 621.16(C₄₃H₂₇NS₂ = 621.82) Sub4-53 m/z = 621.16(C₄₃H₂₇NS₂ = 621.82) Sub4-54 m/z = 671.17(C₄₇H₂₉NS₂ = 671.88) Sub4-55 m/z = 681.21 (C₄₉H₃₁NOS = 681.85) Sub4-56 m/z = 621.16(C₄₃H₂₇NS₂ = 621.82) Sub4-57 m/z = 639.15(C₄₃H₂₆FNS₂ = 639.81) Sub4-58 m/z = 621.16(C₄₃H₂₇NS₂ = 621.82) Sub4-59 m/z = 655.2(C₄₇H₂₉NOS = 655.82) Sub4-60 m/z = 639.22(C₄₇H₂₉NO₂ = 639.75) Sub4-61 m/z = 589.2(C₄₃H₂₇NO2 = 589.69) Sub4-62 m/z = 589.2(C₄₃H₂₇NO₂ = 589.69) Sub4-63 m/z = 605.18(C₄₃H₂₇NOS = 605.76) Sub4-64 m/z = 705.21(C₅₁H₃₁NOS = 705.88) Sub5-1 m/z = 423.16(C₃₁H₂₁NO = 423.52) Sub5-2 m/z = 499.19(C₃₇H₂₅NO = 499.61) Sub5-3 m/z = 575.22(C₄₃H₂₉NO = 575.71) Sub5-4 m/z = 625.24(C₄₇H₃₁NO = 625.77) Sub5-5 m/z = 473.18(C₃₅H₂₃NO = 473.58) Sub5-6 m/z = 655.29(C₄₉H₃₇NO = 655.84) Sub5-7 m/z = 626.24(C₄₆H₃₀N₂O = 626.76) Sub5-8 m/z = 816.31(C₆₁H₄₀N₂O = 817) Sub5-9 m/z = 515.17(C₃₇H₂₅NS = 515.67) Sub5-10 m/z = 591.2(C₄₃H₂₉NS = 591.77) Sub5-11 m/z = 565.19(C₄₁H₂₇NS = 565.73) Sub5-12 m/z = 565.19(C₄₁H₂₇NS = 565.73) Sub5-13 m/z = 615.2(C₄₅H₂₉NS = 615.79) Sub5-14 m/z = 641.22(C₄₇H₃₁NS = 641.83) Sub5-15 m/z = 515.17(C₃₇H₂₅NS = 515.67) Sub5-16 m/z = 641.22(C₄₇H₃₁NS = 641.83) Sub5-17 m/z = 596.23(C₄₃H₂₄D₅NS = 596.8) Sub5-18 m/z = 763.29(C₅₅H₄₁NOS = 764) Sub5-19 m/z = 489.16(C₃₅H₂₃NS = 489.64) Sub5-20 m/z = 641.22(C₄₇H₃₁NS = 641.83)

III. Synthesis of Final Product 1. Synthesis Example of P-1

Sub 1-1 (20 g, 54.5 mmol) was dissolved in a round bottom flask with Toluene (400 mL) and Sub 2-1 (18.3 g, 54.5 mmol), Pd₂(dba)₃ (1.5 g, 1.64 mmol), P(t-Bu)₃ (50 wt % Sol.) (1.3 mL, 3.3 mmol), NaOt-Bu (15.7 g, 163.6 mmol) were added and stirred at 80° C. When the reaction was completed, the solvent was removed, extracted with CH₂Cl₂ and water, the organic layer was dried over MgSO₄, concentrated, and the resulting compound was purified by silica gel column and sublimation to obtain 29.8 g (82% yield) of the product.

2. Synthesis Example of P-73

Sub 1-27 (17 g, 38.4 mmol) and Sub 2-88 (16.4 g, 38.4 mmol), Pd₂(dba)₃ (1.05 g, 1.15 mmol), NaOt-Bu (11.06 g, 115.14 mmol), Anhydrous Toluene (340 mL), P(t-Bu)₃ (50 wt % Sol.) (0.93 mL, 2.3 mmol) were obtained 20.4 g (80% yield) of P-73 using the synthesis method of P-1.

3. Synthesis Example of P-113

Sub 1-87 (12 g, 16.4 mmol) and Sub 2-73 (7.8 g, 16.4 mmol), Pd₂(dba)₃ (0.45 g, 0.5 mmol), NaOt-Bu (4.7 g, 49.2 mmol), anhydrous Toluene (240 mL), P(t-Bu)₃ (50 wt % Sol.) (0.2 mL, 0.98 mmol) were obtained 14.2 g (74% yield) of P-113 using the synthesis method of P-1.

4. Synthesis Example of P-121

Sub 1-105 (12 g, 11.4 mmol) and Sub 2-77 (3.8 g, 11.4 mmol), Pd₂(dba)₃ (0.3 g, 0.34 mmol), NaOt-Bu (3.3 g, 34.3 mmol), anhydrous Toluene (240 mL), P(t-Bu)₃ (50 wt % Sol.) (0.3 mL, 0.7 mmol) were obtained 11.7 g (76% yield) of P-121 using the synthesis method of P-1.

5. Synthesis Example of P-139

Sub 1-160 (9 g, 7.8 mmol) and Sub 2-69 (3.5 g, 7.8 mmol), Pd₂(dba)₃ (0.2 g, 0.23 mmol), NaOt-Bu (2.3 g, 23.5 mmol), anhydrous Toluene (180 mL), P(t-Bu)₃ (50 wt % Sol.) (0.2 mL, 0.5 mmol) were obtained 10.9 g (73% yield) of P-139 using the synthesis method of P-1.

6. Synthesis Example of P 1-2

Sub 1-1 (15 g, 40.9 mmol) and Sub 2-95 (16.0 g, 40.9 mmol), Pd₂(dba)₃ (1.12 g, 1.2 mmol), NaOt-Bu (11.8 g, 122.7 mmol), anhydrous Toluene (300 mL), P(t-Bu)₃ (50 wt % Sol.) (1.00 mL, 2.5 mmol) were obtained 24.2 g (84% yield) of P1-2 using the synthesis method of P-1.

7. Synthesis Example of P 1-13

Sub 1-1 (10.2 g, 27.8 mmol) and Sub 3-12 (12.6 g, 27.8 mmol), Pd₂(dba)₃ (0.8 g, 0.76 mmol), NaOt-Bu (8.0 g, 83.4 mmol), anhydrous Toluene (210 mL), P(t-Bu)₃ (50 wt % Sol.) (0.7 mL, 1.7 mmol) were obtained 17.6 g (81% yield) of P1-13 using the synthesis method of P-1.

8. Synthesis Example of P 2-3

Sub 1-1 (9.5 g, 25.9 mmol) and Sub 4-3 (13.3 g, 25.9 mmol), Pd₂(dba)₃ (0.7 g, 0.8 mmol), NaOt-Bu (7.5 g, 77.7 mmol), anhydrous Toluene (200 mL), P(t-Bu)₃ (50 wt % Sol.) (0.6 mL, 0.8 mmol) were obtained 18.1 g (83% yield) of P2-3 using the synthesis method of P-1.

9. Synthesis Example of P3-3

Sub 1-1 (10.2 g, 27.8 mmol), Sub 5-2 (13.9 g, 27.8 mmol), Pd₂(dba)₃ (1.27 g, 1.39 mmol), NaOt-Bu (8.02 g, 83.4 mmol), anhydrous toluene (204 mL), P(t-Bu)₃ (50 wt % Sol.) (1.13 mL, 2.78 mmol) were obtained by using the synthesis method of P-1 to obtain 17.1 g (yield 74%) of P3-3.

10. Synthesis Example of P3-16

Sub 1-1 (9.10 g, 24.81 mmol), Sub 4-47 (15.03 g, 24.81 mmol), Pd₂(dba)₃ (1.14 g, 1.24 mmol), NaOt-Bu (7.15 g, 74.42 mmol), anhydrous toluene (182 mL), P(t-Bu)₃ (50 wt % Sol.) (1.00 mL, 2.48 mmol) were obtained by using the synthesis method of P-1 to obtain 18.8 g (yield 81%) of P3-16.

11. Synthesis Example of P3-23

Sub 1-1 (8.56 g, 23.33 mmol), Sub 4-56 (14.51 g, 23.33 mmol), Pd₂(dba)₃ (1.07 g, 1.17 mmol), NaOt-Bu (6.73 g, 70.0 mmol), anhydrous Toluene (171 mL), P(t-Bu)₃ (50 wt % Sol.) (0.94 mL, 2.33 mmol) were obtained by using the synthesis method of P-1 to obtain 16.9 g (yield 76%) of P3-23.

Meanwhile, FD-MS values of P-1 to P-139, P1-1 to P1-86, P2-1 to P2-55 and P3-1 to P3-40, the compounds of the present invention prepared according to the synthesis example as described above are shown in Table 3:

TABLE 3 Compound FD-MS compound FD-MS P-1 m/z = 665.24(C₄₉H₃₁NO₂ = 665.79) P-2 m/z = 791.28(C₅₉H₃₇NO₂ = 791.95) P-3 m/z = 891.31(C₆₇H₄₁NO₂ = 892.07) P-4 m/z = 741.27(C₅₅H₃₅NO₂ = 741.89) P-5 m/z = 791.28(C₅₉H₃₇NO₂ = 791.95) P-6 m/z = 665.24(C₄₉H₃₁NO₂ = 665.79) P-7 m/z = 665.24(C₄₉H₃₁NO₂ = 665.79) P-8 m/z = 665.24(C₄₉H₃₁NO₂ = 665.79) P-9 m/z = 665.24(C₄₉H₃₁NO₂ = 665.79) P-10 m/z = 857.33(C₆₄H₄₃NO₂ = 858.05) P-11 m/z = 841.30(C₆₃H₃₉NO₂ = 842.01) P-12 m/z = 817.30(C₆₁H₃₉NO₂ = 817.99) P-13 m/z = 867.31(C₆₅H₄₁NO₂ = 868.05) P-14 m/z = 833.30(C₆₀H₃₉N₃O₂ = 833.99) P-15 m/z = 666.23(C₄₈H₃₀N₂O₂ = 666.78) P-16 m/z = 782.26(C₅₆H₃₄N₂O₃ = 782.90) P-17 m/z = 830.29(C₆₁H₃₈N₂O₂ = 830.99) P-18 m/z = 795.31(C₅₉H₃₃D₄NO₂ = 795.97) P-19 m/z = 812.21(C₅₆H₃₂N₂O₃S = 812.94) P-20 m/z = 897.27(C₆₅H₃₉NO₂S = 898.09) P-21 m/z = 681.21(C₄₉H₃₁NOS = 681.85) P-22 m/z = 807.26(C₅₉H₃₇NOS = 808.01) P-23 m/z = 907.29(C₆₇H₄₁NOS = 908.13) P-24 m/z = 807.26(C₅₉H₃₇NOS = 808.01) P-25 m/z = 805.24(C₅₉H₃₅NOS = 806.00) P-26 m/z = 797.28(C₅₈H₃₉NOS = 798.02) P-27 m/z = 757.24(C₅₅H₃₅NOS = 757.95) P-28 m/z = 771.22(C₅₅H₃₃NO₂S = 771.93) P-29 m/z = 757.24(C₅₅H₃₅NOS = 757.95) P-30 m/z = 787.20(C₅₅H₃₃NOS₂ = 788.00) P-31 m/z = 857.28(C₆₃H₃₉NOS = 858.07) P-32 m/z = 833.28(C₆₁H₃₉NOS = 834.05) P-33 m/z = 883.29(C₆₅H₄₁NOS = 884.11) P-34 m/z = 781.24(C₅₇H₃₅NOS = 781.97) P-35 m/z = 682.21(C₄₈H₃₀N₂OS = 682.84) P-36 m/z = 681.21(C₄₉H₃₁NOS = 681.85) P-37 m/z = 807.26(C₅₉H₃₇NOS = 808.01) P-38 m/z = 907.29(C₆₇H₄₁NOS = 908.13) P-39 m/z = 807.26(C₅₉H₃₇NOS = 808.01) P-40 m/z = 807.26(C₅₉H₃₇NOS = 808.01) P-41 m/z = 681.21(C₄₉H₃₁NOS = 681.85) P-42 m/z = 681.21(C₄₉H₃₁NOS = 681.85) P-43 m/z = 681.21(C₄₉H₃₁NOS = 681.85) P-44 m/z = 681.21(C₄₉H₃₁NOS = 681.85) P-45 m/z = 873.31(C₆₄H₄₃NOS = 874.11) P-46 m/z = 857.28(C₆₃H₃₉NOS = 858.07) P-47 m/z = 833.28(C₆₁H₃₉NOS = 834.05) P-48 m/z = 883.29(C₆₅H₄₁NOS = 884.11) P-49 m/z = 781.24(C₅₇H₃₅NOS = 781.97) P-50 m/z = 682.21(C₄₈H₃₀N₂OS = 682.84) P-51 m/z = 798.23(C₅₆H₃₄N₂O₂S = 798.96) P-52 m/z = 846.27(C₆₁H₃₈N₂OS = 847.05) P-53 m/z = 811.28(C₅₉H₃₃D₄NOS = 812.04) P-54 m/z = 828.19(C₅₆H₃₂N₂O₂S₂ = 829.00) P-55 m/z = 863.23(C₆₁H₃₇NOS₂ = 864.09) P-56 m/z = 823.24(C₅₉H₃₇NS₂ = 824.07) P-57 m/z = 863.23(C₆₁H₃₇NOS₂ = 864.09) P-58 m/z = 929.22(C₆₅H₃₉NS₃ = 930.21) P-59 m/z = 938.28(C₆₇H₄₂N₂S₂ = 939.21) P-60 m/z = 797.22(C₅₇H₃₅NS₂ = 798.03) P-61 m/z = 813.25(C₅₈H₃₉NS₂ = 814.08) P-62 m/z = 773.22(C₅₅H₃₅NS₂ = 774.01) P-63 m/z = 747.21(C₅₃H₃₃NS₂ = 747.97) P-64 m/z = 823.24(C₅₉H₃₇NS₂ = 824.07) P-65 m/z = 853.19(C₅₉H₃₅NS₃ = 854.12) P-66 m/z = 923.27(C₆₇H₄₁NS₂ = 924.19) P-67 m/z = 949.28(C₆₉H₄₃NS₂ = 950.23) P-68 m/z = 781.24(C₅₇H₃₅NOS = 781.97) P-69 m/z = 847.24(C₆₁H₃₇NS₂ = 848.09) P-70 m/z = 698.19(C₄₈H₃₀N₂S₂ = 698.90) P-71 m/z = 874.27(C₆₂H₃₈N₂O₂S = 875.06) P-72 m/z = 872.29(C₆₃H₄₀N₂OS = 873.09) P-73 m/z = 833.28(C₆₁H₃₉NOS = 834.05) P-74 m/z = 970.21(C₆₆H₃₈N₂OS₃ = 971.22) P-75 m/z = 1055.33(C₇₆H₄₉NOS₂ = 1056.35) P-76 m/z = 741.27(C₅₅H₃₅NO₂ = 741.89) P-77 m/z = 883.29(C₆₅H₄₁NOS = 884.11) P-78 m/z = 931.31(C₆₉H₄₁NO₃ = 932.09) P-79 m/z = 868.31(C₆₄H₄₀N₂O₂ = 869.04) P-80 m/z = 841.30(C₆₃H₃₉NO₂ = 842.01) P-81 m/z = 922.32(C₆₇H₄₂N₂O₃ = 923.08) P-82 m/z = 1124.40(C₈₃H₅₂N₂O₃ = 1125.34) P-83 m/z = 1164.43(C₈₆H₅₆N₂O₃ = 1165.41) P-84 m/z = 1124.40(C₈₃H₅₂N₂O₃ = 1125.34) P-85 m/z = 1014.33(C₇₃H₄₆N₂O₂S = 1015.24) P-86 m/z = 1154.35(C₈₃H₅₀N₂O₃S = 1155.38) P-87 m/z = 1115.41(C₈₁H₅₃N₃O₃ = 1116.33) P-88 m/z = 1140.43(C₈₄H₅₆N₂O₃ = 1141.38) P-89 m/z = 1104.34(C₇₉H₄₈N₂O₃S = 1105.32) P-90 m/z = 1074.38(C₇₉H₅₀N₂O₃ = 1075.28) P-91 m/z = 1038.38(C₇₆H₅₀N₂O₃ = 1039.25) P-92 m/z = 1235.38(C₈₇H₅₃N₃O₄S = 1236.46) P-93 m/z = 1154.35(C₈₃H₅₀N₂O₃S = 1155.38) P-94 m/z = 1196.40(C₈₆H₅₆N₂O₃S = 1197.47) P-95 m/z = 1296.43(C₉₄H₆₀N₂O₃S = 1297.59) P-96 m/z = 1232.38(C₈₉H₅₆N₂OS₂ = 1233.56) P-97 m/z = 1196.35(C₈₅H₅₂N₂O₂S₂ = 1197.48) P-98 m/z = 1154.35(C₈₃H₅₀N₂O₃S = 1155.38) P-99 m/z = 1443.45(C₁₀₂H₆₅N₃O₃S₂ = 1444.78) P-100 m/z = 1190.44(C₈₈H₅₈N₂O₃ = 1191.44) P-101 m/z = 938.30(C₆₇H₄₂N₂O₂S = 939.15) P-102 m/z = 1140.37(C₈₃H₅₂N₂O₂S = 1141.40) P-103 m/z = 1180.41(C₈₆H₅₆N₂O₂S = 1181.47) P-104 m/z = 1216.41(C₈₉H₅₆N₂O₂S = 1217.50) P-105 m/z = 1030.31(C₇₃H₄₆N₂OS₂ = 1031.30) P-106 m/z = 1170.33(C₈₃H₅₀N₂O₂S₂ = 1171.45) P-107 m/z = 1131.39(C₈₁H₅₃N₃O₂S = 1132.39) P-108 m/z = 1188.36(C₈₄H₅₆N₂S₃ = 1189.57) P-109 m/z = 1120.32(C₇₉H₄₈N₂O₂S₂ = 1121.39) P-110 m/z = 1090.36(C₇₉H₅₀N₂O₂S = 1091.34) P-111 m/z = 1070.34(C₇₆H₅₀N₂OS₂ = 1071.37) P-112 m/z = 1251.35(C₈₇H₅₃N₃O₃S₂ = 1252.52) P-113 m/z = 1170.33(C₈₃H₅₀N₂O₂S₂ = 1171.45) P-114 m/z = 1246.42(C₉₀H₅₈N₂O₃S = 1247.53) P-115 m/z = 1346.45(C₉₈H₆₂N₂O₃S = 1347.65) P-116 m/z = 1216.41(C₈₉H₅₆N₂O₂S = 1217.50) P-117 m/z = 1271.39(C₉₁H₅₇N₃OS₂ = 1272.60) P-118 m/z = 1170.33(C₈₃H₅₀N₂O₂S₂ = 1171.45) P-119 m/z = 1459.42(C₁₀₂H₆₅N₃O₂S₃ = 1460.84) P-120 m/z = 1206.42(C₈₈H₅₈N₂O₂S = 1207.50) P-121 m/z = 1347.44(C₉₇H₆₁N₃O₃S = 1348.63) P-122 m/z = 1579.48(C₁₁₃H₆₉N₃O₃S₂ = 1580.93) P-123 m/z = 1705.58(C₁₂₄H₇₉N₃O₄S = 1707.07) P-124 m/z = 1489.47(C₁₀₇H₆₇N₃O₂S₂ = 1490.85) P-125 m/z = 1453.43(C₁₀₃H₆₃N₃O₃S₂ = 1454.78) P-126 m/z = 1619.51(C₁₁₆H₇₃N₃O₃S₂ = 1621.00) P-127 m/z = 1456.42(C₁₀₂H₆₄N₄OS₃ = 1457.84) P-128 m/z = 1565.50(C₁₁₃H₇₁N₃O₂S₂ = 1566.95) P-129 m/z = 1528.48(C₁₀₉H₆₈N₄O₂S₂ = 1529.89) P-130 m/z = 1519.42(C₁₀₇H₆₅N₃O₂S₃ = 1520.90) P-131 m/z = 1826.61(C₁₃₁H₈₆N₄O₃S₂ = 1828.27) P-132 m/z = 1555.51(C₁₁₂H₇₃N₃O₂S₂ = 1556.96) P-133 m/z = 1439.45(C₁₀₃H₆₅N₃O₂S₂ = 1440.79) P-134 m/z = 1595.46(C₁₁₃H₆₉N₃O₂S₃ = 1596.99) P-135 m/z = 1721.56(C₁₂₄H₇₉N₃O₃S₂ = 1723.13) P-136 m/z = 1571.44(C₁₁₁H₆₉N₃S₄ = 1573.03) P-137 m/z = 1898.71(C₁₃₃H₁₀₂N₄O₃S₃ = 1900.48) P-138 m/z = 1812.54(C₁₂₉H₈₀N₄O₂S₃ = 1814.27) P-139 m/z = 1914.69(C₁₃₃H₁₀₂N₄O₂S₄ = 1916.55) P1-1 m/z = 705.27(C₅₂H₃₅NO₂ = 705.86) P1-2 m/z = 705.27(C₅₂H₃₅NO₂ = 705.86) P1-3 m/z = 705.27(C₅₂H₃₅NO₂ = 705.86) P1-4 m/z = 705.27(C₅₂H₃₅NO₂ = 705.86) P1-5 m/z = 721.24(C₅₂H₃₅NOS = 721.92) P1-6 m/z = 829.30(C₆₂H₃₉NO₂ = 830.00) P1-7 m/z = 829.30(C₆₂H₃₉NO₂ = 830.00) P1-8 m/z = 829.30(C₆₂H₃₉NO₂ = 830.00) P1-9 m/z = 829.30(C₆₂H₃₉NO₂ = 830.00) P1-10 m/z = 845.28(C₆₂H₃₉NOS = 846.06) P1-11 m/z = 827.28(C₆₂H₃₇NO₂ = 827.98) P1-12 m/z = 843.26(C₆₂H₃₇NOS = 844.04) P1-13 m/z = 781.30(C₅₈H₃₉NO₂ = 781.96) P1-14 m/z = 797.28(C₅₈H₃₉NOS = 798.02) P1-15 m/z = 781.30(C₅₈H₃₉NO₂ = 781.96) P1-16 m/z = 797.28(C₅₈H₃₉NOS = 798.02) P1-17 m/z = 781.30(C₅₈H₃₉NO₂ = 781.96) P1-18 m/z = 797.28(C₅₈H₃₉NOS = 798.02) P1-19 m/z = 781.30(C₅₈H₃₉NO₂ = 781.96) P1-20 m/z = 781.30(C₅₈H₃₉NO₂ = 781.96) P1-21 m/z = 781.30(C₅₈H₃₉NO₂ = 781.96) P1-22 m/z = 781.30(C₅₈H₃₉NO₂ = 781.96) P1-23 m/z = 797.28(C₅₈H₃₉NOS = 798.02) P1-24 m/z = 797.28(C₅₈H₃₉NOS = 798.02) P1-25 m/z = 797.28(C₅₈H₃₉NOS = 798.02) P1-26 m/z = 831.31(C₆₂H₄₁NO₂ = 832.02) P1-27 m/z = 847.29(C₆₂H₄₁NOS = 848.08) P1-28 m/z = 831.31(C₆₂H₄₁NO₂ = 832.02) P1-29 m/z = 847.29(C₆₂H₄₁NOS = 848.08) P1-30 m/z = 831.31(C₆₂H₄₁NO₂ = 832.02) P1-31 m/z = 847.29(C₆₂H₄₁NOS = 848.08) P1-32 m/z = 782.29(C₅₇H₃₈N₂O₂ = 782.94) P1-33 m/z = 913.34(C₆₇H₄₇NOS = 914.18) P1-34 m/z = 855.31(C₆₄H₄₁NO₂ = 856.04) P1-35 m/z = 849.30(C₆₂H₃₅D₄NOS = 850.08) P1-36 m/z = 857.33(C₆₄H₄₃NO₂ = 858.05) P1-37 m/z = 873.31(C₆₄H₄₃NOS = 874.11) P1-38 m/z = 857.33(C₆₄H₄₃NO₂ = 858.05) P1-39 m/z = 873.31(C₆₄H₄₃NOS = 874.11) P1-40 m/z = 873.31(C₆₄H₄₃NOS = 874.11) P1-41 m/z = 857.33(C₆₄H₄₃NO₂ = 858.05) P1-42 m/z = 857.33(C₆₄H₄₃NO₂ = 858.05) P1-43 m/z = 857.33(C₆₄H₄₃NO₂ = 858.05) P1-44 m/z = 873.31(C₆₄H₄₃NOS = 874.11) P1-45 m/z = 873.31(C₆₄H₄₃NOS = 874.11) P1-46 m/z = 797.28(C₅₈H₃₉NOS = 798.02) P1-47 m/z = 721.24(C₅₂H₃₅NOS = 721.92) P1-48 m/z = 721.24(C₅₂H₃₅NOS = 721.92) P1-49 m/z = 721.24(C₅₂H₃₅NOS = 721.92) P1-50 m/z = 737.22(C₅₂H₃₅NS₂ = 737.98) P1-51 m/z = 845.28(C₆₂H₃₉NOS = 846.06) P1-52 m/z = 861.25(C₆₂H₃₉NS₂ = 862.12) P1-53 m/z = 861.25(C₆₂H₃₉NS₂ = 862.12) P1-54 m/z = 861.25(C₆₂H₃₉NS₂ = 862.12) P1-55 m/z = 861.25(C₆₂H₃₉NS₂ = 862.12) P1-56 m/z = 921.28(C₆₆H₃₉N₃OS = 922.12) P1-57 m/z = 859.24(C₆₂H₃₇NS₂ = 860.11) P1-58 m/z = 797.28(C₅₈H₃₉NOS = 798.02) P1-59 m/z = 813.25(C₅₈H₃₉NS₂ = 814.08) P1-60 m/z = 797.28(C₅₈H₃₉NOS = 798.02) P1-61 m/z = 813.25(C₅₈H₃₉NS₂ = 814.08) P1-62 m/z = 797.28(C₅₈H₃₉NOS = 798.02) P1-63 m/z = 813.25(C₅₈H₃₉NS₂ = 814.08) P1-64 m/z = 797.28(C₅₈H₃₉NOS = 798.02) P1-65 m/z = 813.25(C₅₈H₃₉NS₂ = 814.08) P1-66 m/z = 847.29(C₆₂H₄₁NOS = 848.08) P1-67 m/z = 863.27(C₆₂H₄₁NS₂ = 864.14) P1-68 m/z = 847.29(C₆₂H₄₁NOS = 848.08) P1-69 m/z = 863.27(C₆₂H₄₁NS₂ = 864.14) P1-70 m/z = 847.29(C₆₂H₄₁NOS = 848.08) P1-71 m/z = 863.27(C₆₂H₄₁NS₂ = 864.14) P1-72 m/z = 798.27(C₅₇H₃₈N₂OS = 799.00) P1-73 m/z = 797.28(C₅₈H₃₉NOS = 798.02) P1-74 m/z = 787.24(C₅₆H₃₇NS₂ = 788.04) P1-75 m/z = 787.24(C₅₆H₃₇NS₂ = 788.04) P1-76 m/z = 771.26(C₅₆H₃₇NOS = 771.98) P1-77 m/z = 771.26(C₅₆H₃₇NOS = 771.98) P1-78 m/z = 813.25(C₅₈H₃₉NS₂ = 814.08) P1-79 m/z = 907.35(C₆₈H₄₅NO₂ = 908.11) P1-80 m/z = 903.31(C₆₈H₄₁NO₂ = 904.08) P1-81 m/z = 827.28(C₆₂H₃₇NO₂ = 827.98) P1-82 m/z = 843.26(C₆₂H₃₇NOS = 844.04) P1-83 m/z = 843.26(C₆₂H₃₇NOS = 844.04) P1-84 m/z = 787.24(C₅₆H₃₇NS₂ = 788.04) P1-85 m/z = 879.31(C₆₆H₄₁NO₂ = 880.06) P1-86 m/z = 781.30(C₅₈H₃₉NO₂ = 781.96) P2-1 m/z = 843.28(C₆₂H₃₇NO₃ = 843.98) P2-2 m/z = 843.28(C₆₂H₃₇NO₃ = 843.98) P2-3 m/z = 843.28(C₆₂H₃₇NO₃ = 843.98) P2-4 m/z = 843.28(C₆₂H₃₇NO₃ = 843.98) P2-5 m/z = 909.27(C₆₆H₃₉NO₂S = 910.10) P2-6 m/z = 861.27(C₆₂H₃₆FNO₃ = 861.97) P2-7 m/z = 893.29(C₆₆H₃₉NO₃ = 894.04) P2-8 m/z = 995.34(C₇₄H₄₅NO₃ = 996.18) P2-9 m/z = 859.25(C₆₂H₃₇NO₂S = 860.04) P2-10 m/z = 859.25(C₆₂H₃₇NO₂S = 860.04) P2-11 m/z = 859.25(C₆₂H₃₇NO₂S = 860.04) P2-12 m/z = 859.25(C₆₂H₃₇NO₂S = 860.04) P2-13 m/z = 859.25(C₆₂H₃₇NO₂S = 860.04) P2-14 m/z = 859.25(C₆₂H₃₇NO₂S = 860.04) P2-15 m/z = 859.25(C₆₂H₃₇NO₂S = 860.04) P2-16 m/z = 859.25(C₆₂H₃₇NO₂S = 860.04) P2-17 m/z = 875.23(C₆₂H₃₇NOS₂ = 876.10) P2-18 m/z = 875.23(C₆₂H₃₇NOS₂ = 876.1) P2-19 m/z = 891.21(C₆₂H₃₇NS₃ = 892.17) P2-20 m/z = 919.31(C₆₈H₄₁NO₃ = 920.08) P2-21 m/z = 935.29(C₆₈H₄₁NO₂S = 936.14) P2-22 m/z = 951.26(C₆₈H₄₁NOS₂ = 952.20) P2-23 m/z = 967.24(C₆₈H₄₁NS₃ = 968.26) P2-24 m/z = 985.30(C₇₂H₄₃NO₂S = 986.20) P2-25 m/z = 1001.28(C₇₂H₄₃NOS₂ = 1002.26) P2-26 m/z = 952.26(C₆₇H₄₀N₂OS₂ = 953.19) P2-27 m/z = 952.26(C₆₇H₄₀N₂OS₂ = 953.19) P2-28 m/z = 919.31(C₆₈H₄₁NO₃ = 920.08) P2-29 m/z = 935.29(C₆₈H₄₁NO₂S = 936.14) P2-30 m/z = 919.31(C₆₈H₄₁NO₃ = 920.08) P2-31 m/z = 935.29(C₆₈H₄₁NO₂S = 936.14) P2-32 m/z = 935.29(C₆₈H₄₁NO₂S = 936.14) P2-33 m/z = 967.24(C₆₈H₄₁NS₃ = 968.26) P2-34 m/z = 900.23(C₆₃H₃₆N₂OS₂ = 901.11) P2-35 m/z = 901.25(C₆₄H₃₉NOS₂ = 902.14) P2-36 m/z = 893.29(C₆₆H₃₉NO₃ = 894.04) P2-37 m/z = 941.22(C₆₆H₃₉NS₃ = 942.23) P2-38 m/z = 909.27(C₆₆H₃₉N0₂S = 910.10) P2-39 m/z = 919.31(C₆₈H₄₁NO₃ = 920.08) P2-40 m/z = 941.22(C₆₆H₃₉NS₃ = 942.23) P2-41 m/z = 909.27(C₆₆H₃₉NO₂S = 910.1) P2-42 m/z = 893.29(C₆₆H₃₉NO₃ = 894.04) P2-43 m/z = 941.22(C₆₆H₃₉NS₃ = 942.23) P2-44 m/z = 909.27(C₆₆H₃₉NO₂S = 910.10) P2-45 m/z = 893.29(C₆₆H₃₉NO₃ = 894.04) P2-46 m/z = 951.26(C₆₈H₄₁NOS₂ = 952.2) P2-47 m/z = 1017.26(C₇₂H₄₃NS₃ = 1018.32) P2-48 m/z = 995.34(C₇₄H₄₅NO₃ = 996.18) P2-49 m/z = 895.23(C₆₂H₃₃D₄NS₃ = 896.19) P2-50 m/z = 995.34(C₇₄H₄₅NO₃ = 996.18) P2-51 m/z = 995.34(C₇₄H₄₅NO₃ = 996.18) P2-52 m/z = 1093.29(C₇₈H₄₇NS₃ = 1094.42) P2-53 m/z = 975.26(C₇₀H₄₁NOS₂ = 976.22) P2-54 m/z = 991.24(C₇₀H₄₁NS₃ = 992.29) P2-55 m/z = 943.31(C₇₀H₄₁NO₃ = 944.10) P3-1 m/z = 753.27(C₅₆H₃₅NO₂ = 753.9) P3-2 m/z = 845.28(C₆₂H₃₉NOS = 846.06) P3-3 m/z = 829.3(C₆₂H₃₉NO₂ = 830) P3-4 m/z = 803.28(C₆₀H₃₇NO₂ = 803.96) P3-5 m/z = 911.27(C₆₆H₄₁NS₂ = 912.18) P3-6 m/z = 985.39(C₇₄H₅₁NO₂ = 986.23) P3-7 m/z = 995.32(C₇₄H₄₅NOS = 996.24) P3-8 m/z = 956.34(C₇₁H₄₄N₂O₂ = 957.15) P3-9 m/z = 945.31 (C₇₀H₄₃NOS = 946.18) P3-10 m/z = 971.32(C₇₂H₄₅NOS = 972.22) P3-11 m/z = 921.31(C₆₈H₄₃NOS = 922.16) P3-12 m/z = 905.33(C₆₈H₄₃NO₂ = 906.1) P3-13 m/z = 955.35(C₇₂H₄₅NO₂ = 956.16) P3-14 m/z = 1146.42(C₈₆H₅₄N₂O₂ = 1147.39) P3-15 m/z = 940.32(C₆₈H₃₆D₅NO₂S = 941.17) P3-16 m/z = 935.29(C₆₈H₄₁NO₂S = 936.14) P3-17 m/z = 919.31(C₆₈H₄₁NO₃ = 920.08) P3-18 m/z = 919.31(C₆₈H₄₁NO₃ = 920.08) P3-19 m/z = 1017.26(C₇₂H₄₃NS₃ = 1018.32) P3-20 m/z = 951.26(C₆₈H₄₁NOS₂ = 952.2) P3-21 m/z = 967.24(C₆₈H₄₁NS₃ = 968.26) P3-22 m/z = 951.26(C₆₈H₄₁NOS₂ = 952.2) P3-23 m/z = 951.26(C₆₈H₄₁NOS₂ = 952.2) P3-24 m/z = 951.26(C₆₈H₄₁NOS₂ = 952.2) P3-25 m/z = 953.28(C₆₈H₄₀FNO₂S = 954.13) P3-26 m/z = 861.25(C₆₂H₃₉NS₂ = 862.12) P3-27 m/z = 971.32(C₇₂H₄₅NOS = 972.22) P3-28 m/z = 942.32(C₆₈H₃₈D₅NS₂ = 943.25) P3-29 m/z = 11 09.37(C₈₀H₅₅NOS₂ = 1110.45) P3-30 m/z = 969.25(C₆₈H₄₀FNOS₂ = 970.19) P3-31 m/z = 967.24(C₆₈H₄₁NS₃ = 968.26) P3-32 m/z = 969.32(C₇₂H₄₃NO₃ = 970.14) P3-33 m/z = 1103.33(C₈₀H₄₉NOS₂ = 1104.4) P3-34 m/z = 1001.28(C₇₂H₄₃NOS₂ = 1002.26) P3-35 m/z = 835.24(C₆₀H₃₇NS₂ = 836.08) P3-36 m/z = 1047.35(C₇₈H₄₉NOS = 1048.32) P3-37 m/z = 1027.31(C₇₄H₄₅NO₃S = 1028.24) P3-38 m/z = 991.35(C₇₂H₄₉NO₂S = 992.25) P3-39 m/z = 919.31(C₆₈H₄₁NO₃ = 920.08) P3-40 m/z = 1051.29(C₇₆H₄₅NOS₂ = 1052.32)

Evaluation of Manufacture of Organic Electronic Element [Example 1] Red Organic Light Emitting Diode (Emitting Auxiliary Layer)

An organic light emitting diode was manufactured according to a conventional method using the compound of the present invention as an emitting auxiliary layer material. First, a hole injection layer was formed by vacuum depositing 4,4′,4″-Tris[2-naphthyl(phenyl)amino]triphenylamine (hereinafter, 2-TNATA) to a thickness of 60 nm on an ITO layer (anode) formed on a glass substrate, and a hole transport layer was formed by vacuum deposition of N,N′-bis(1-naphthalenyl)-N,N′-bis-phenyl-(1,1′-biphenyl)-4,4′-diamine (hereinafter, NPB) to a thickness of 60 nm on the hole injection layer. Subsequently, compound PA-1 was vacuum-deposited to a thickness of 20 nm on the hole transport layer to form an emission auxiliary layer, 4,4′-N,N′-dicarbazole-biphenyl (hereinafter, CBP) was used as a host material and bis-(1-phenylisoquinolyl)iridium(III)acetylacetonate (hereinafter, (piq)2Ir(acac)) was used as a dopant material on the emitting auxiliary layer, doped at a weight ratio of 95:5, and vacuum deposited to a thickness of 30 nm to form an emitting layer.

Subsequently, (1,1′-biphenyl-4-olato)bis(2-methyl-8-quinolinolato)aluminum (hereinafter, BAlq) was vacuum deposited to a thickness of 10 nm on the emitting layer to form a hole blocking layer, an electron transport layer was formed by vacuum depositing tris-(8-hydroxyquinoline)aluminum (hereinafter, Alq₃) to a thickness of 40 nm on the hole blocking layer. Thereafter, an electron injection layer was formed by depositing LiF, an alkali metal halide, to a thickness of 0.2 nm, then, Al was deposited to a thickness of 150 nm to form a cathode, thereby manufacturing an organic light emitting diode.

[Example 2] to [Example 21] Red Organic Light Emitting Diode (Emitting Auxiliary Layer)

An organic light emitting diode was manufactured in the same manner as in Example 1, except that the compound PA-2 and the compound of the present invention described in Table 4 below were used instead of the compound PA-1 as the emitting auxiliary layer material.

Comparative Example 1

An organic light emitting diode was manufactured in the same manner as in Example 1, except that the comparative example 1 below were used instead of the compound PA-1 as the emitting auxiliary layer material.

Comparative Example 1

Electroluminescence (EL) characteristics were measured by PR-650 of photoresearch company by applying a forward bias direct current voltage to the organic light emitting diodes prepared according to Examples 1 to 21 and Comparative Example 1 of the present invention, T95 life was measured through a life measurement equipment manufactured by McScience at a luminance of 2500 cd/m², and the measurement results are shown in Table 4 below.

TABLE 4 Voltage Current Density Brightness Efficiency Lifetime CIE compound (V) (mA/cm²) (cd/m²) (cd/A) T(95) x y comparative Comparative 6.3 26.6 2500.0 9.4 75.6 0.64 0.31 example(1) compound 1 example(1) PA-1 6.0 21.9 2500.0 11.4 98.3 0.63 0.35 example(2) PA-2 5.6 18.1 2500.0 13.8 110.5 0.61 0.31 example(3) P-1 4.8 11.1 2500.0 22.6 116.4 0.64 0.30 example(4) P-4 4.9 10.3 2500.0 24.3 112.7 0.63 0.31 example(5) P-12 4.8 9.7 2500.0 25.7 118.3 0.62 0.30 example(6) P-14 4.9 9.7 2500.0 25.9 117.2 0.61 0.31 example(7) P-22 4.8 9.7 2500.0 25.7 119.0 0.64 0.30 example(8) P-30 5.0 10.7 2500.0 23.5 113.4 0.65 0.35 example(9) P-37 4.9 10.8 2500.0 23.2 116.9 0.62 0.33 example(10) P-57 5.2 10.9 2500.0 22.9 112.0 0.64 0.32 example(11) P-59 5.2 9.7 2500.0 25.9 115.4 0.61 0.30 example(12) P-68 5.2 10.6 2500.0 23.6 114.7 0.64 0.30 example(13) P-77 5.1 10.3 2500.0 24.4 119.5 0.61 0.30 example(14) P-81 5.0 11.6 2500.0 21.6 122.8 0.62 0.30 example(15) P-82 5.2 11.9 2500.0 21.1 120.7 0.63 0.30 example(16) P-94 5.1 11.5 2500.0 21.8 120.9 0.65 0.32 example(17) P-109 5.0 11.6 2500.0 21.5 120.8 0.63 0.35 example(18) P-115 5.2 11.1 2500.0 22.6 123.9 0.62 0.31 example(19) P-124 5.3 12.0 2500.0 20.8 124.1 0.60 0.34 example(20) P-136 5.3 12.3 2500.0 20.3 126.7 0.63 0.34 example(21) P-138 5.3 12.4 2500.0 20.2 127.3 0.64 0.35

As can be seen from the results in Table 4, when a red organic light emitting diode is manufactured using the material for an organic light emitting diode of the present invention as a phosphorescent host material, compared to the case of using the compound PA-1, the compound PA-2, and the comparative compound 1, the driving voltage of the organic light emitting diode could be lowered and the efficiency and lifespan were significantly improved.

In detail, the comparative compound and the compound of the present invention are the same in that they contain a xanthene core and an amine substituent, the device result of compound PA-1 substituted with dibenzofuran was improved compared to Comparative Compound 1 in which a simple aryl group was substituted with the substituent of the amine group, and the device result of compound PA-2 with more secondary substituents bonded was more improved. Also, the compound PA-2 and the compound of the present invention differ in the bonding position of the secondary substituent of the amine substituent, dibenzofuran or dibenzothiophene. In other words, it was confirmed that the compound of the present invention, in which an amine group and a secondary substituent group are bonded to the same ring in dibenzofuran or dibenzothiophene, exhibits more improved device performance than compound PA-2.

This result shows that the difference in hole mobility is large depending on the bonding position of the substituent, and this difference in mobility affects the overall device.

By using the compound of the present invention as an emitting auxiliary layer, the HOMO or LUMO energy level of the compound of the present invention has an appropriate value between the hole transport layer and the emitting layer, as a result, holes and electrons achieve a charge balance, and light emission occurs inside the emitting layer rather than at the interface of the hole transport layer, maximizing efficiency and lifespan.

Meanwhile, comparing the results of the embodiments of the present invention, it can be seen that there are differences in driving voltage and luminous efficiency according to the bonding position and type of the secondary substituent, and different lifespan results are produced depending on the number of substitutions of amino groups in the central core.

In conclusion, the physical properties of the compound such as hole characteristics, light efficiency characteristics, energy level (LUMO, HOMO level, T1 level), hole injection & mobility characteristics, and electron blocking characteristics vary depending on the substituent, resulting in completely different device results.

[Example 22] Green Organic Light Emitting Diode (Emitting Auxiliary Layer)

2-TNATA was vacuum-deposited to a thickness of 60 nm on the ITO layer (anode) formed on the glass substrate to form a hole injection layer, and then NPB was vacuum-deposited to a thickness of 60 nm on the hole injection layer to form a hole transport layer. Subsequently, the following compound PA-3 was vacuum-deposited to a thickness of 20 nm on the hole transport layer to form an emitting auxiliary layer, and on the emitting auxiliary layer, CBP was used as a host material and tris(2-phenylpyridine)-iridium (hereinafter, Ir(ppy)₃) was used as a dopant material, doped at a weight ratio of 95:5, and vacuum deposited to a thickness of 30 nm to form an emitting layer. Then, BAlq was vacuum-deposited to a thickness of 10 nm on the emitting layer to form a hole blocking layer, Alq₃ was vacuum deposited on the hole blocking layer to a thickness of 40 nm on the hole blocking layer to form an electron transport layer. Thereafter, an electron injection layer was formed by depositing LiF, an alkali metal halide, to a thickness of 0.2 nm, and subsequently, Al was deposited to a thickness of 150 nm to form a cathode, thereby manufacturing an organic light emitting diode.

[Example 23] to [Example 35] Green Organic Light Emitting Diode (Emitting Auxiliary Layer)

An organic light emitting diode was manufactured in the same manner as in Example 22, except that the compound of the present invention described in Table 5 below was used instead of the compound PA-3 as the emitting auxiliary layer material.

[Comparative Example 2] and [Comparative Example 3]

An organic light emitting diode was manufactured in the same manner as in Example 22, except that Comparative Compound 2 and Comparative Compound 3 were used, respectively, instead of the compound PA-3 as the emitting auxiliary layer material.

Electroluminescence (EL) characteristics were measured by PR-650 of photoresearch company by applying a forward bias direct current voltage to the organic light emitting diode prepared according to Examples 22 to 35 and Comparative Example 2 to 3 of the present invention, T95 life was measured through a life measurement equipment manufactured by McScience at a luminance of 5000 cd/m², and the measurement results are shown in Table 5 below.

TABLE 5 Voltage Current Density Brightness Efficiency Lifetime CIE compound (V) (mA/cm²) (cd/m²) (cd/A) T(95) x y comparative comparative 6.3 36.2 5000.0 13.8 75.6 0.30 0.61 example (2) compound 2 comparative comparative 6.1 25.6 5000.0 19.5 75.9 0.30 0.60 example (3) compound 3 example(22) PA-3 5.6 24.5 5000.0 20.4 103.3 0.32 0.65 example(23) P1-2 5.0 10.1 5000.0 49.7 139.6 0.32 0.62 example(24) P1-5 5.2 12.7 5000.0 39.4 129.3 0.32 0.61 example(25) P1-6 5.1 11.7 5000.0 42.9 135.6 0.33 0.60 example(26) P1-12 5.2 12.6 5000.0 39.6 130.5 0.31 0.64 example(27) P1-20 5.2 12.4 5000.0 40.2 129.5 0.33 0.61 example(28) P1-44 5.1 11.4 5000.0 43.9 137.0 0.31 0.60 example(29) P1-50 5.1 12.6 5000.0 39.5 129.7 0.30 0.62 example(30) P1-55 5.1 10.6 5000.0 47.2 137.3 0.31 0.64 example(31) P1-73 5.0 12.1 5000.0 41.2 136.2 0.33 0.61 example(32) P1-77 5.3 11.3 5000.0 44.3 129.7 0.35 0.61 example(33) P1-78 5.0 11.9 5000.0 42.2 132.6 0.32 0.61 example(34) P1-84 5.3 13.8 5000.0 36.2 127.3 0.33 0.62 example(35) P1-85 5.3 14.1 5000.0 35.5 127.6 0.32 0.63

As can be seen from the results in Table 5, when a green organic light emitting diode is manufactured using the material for an organic light emitting diode of the present invention as an emitting auxiliary layer material, compared to the case of using the comparative compound 2, the comparative compound 3, the compound PA-3, and the driving voltage of the organic light emitting diode could be lowered and the efficiency and lifespan were significantly improved.

Specifically, in the case of a comparative compound, the device results using Comparative Compound 3 with arylamine bonded at the 2 position of the xanthene core, compared to Comparative Compound 2 with arylamine bonded at the 3 position of the xanthene core, improved efficiency. Also, it can be seen that the device result of the compound PA-3 in which a heterocyclic compound such as dibenzofuran is bonded as a substituent of an amine group is improved as a whole.

The compound of the present invention is a compound characterized in that an amine group is bonded to 2 position of the xanthene core, and dibenzofuran or 1 substituted dibenzothiophene is bonded as a substituent of the amine group bonded to the core, it can be seen that the device results of Examples 23 to 35 made of the compounds of the present invention having such characteristics are remarkably excellent.

These results can be explained by the HOMO values of Comparative Compound 2, Comparative Compound 3, Compound PA-3, and the present compound. Referring to Table 6 below, it can be seen that the HOMO value of Comparative Compound 3 in which an amine group is bonded at the 2 position of the core is higher than Comparative Compound 2 in which an amine group is bonded at the 3 position of the core. Also, it can be seen that the HOMO value of Compound P-14 of the present invention in which the amine group is bonded to the 2 position of the core and 1 substituted dibenzofuran is bonded as a substituent of the bonded amine group is the highest, compared to the compound PA-3 in which an amine group is bonded to the 3 position of the core and 3 substituted dibenzofuran is bonded as a substituent of the bonded amine group.

TABLE 6 comparative comparative compound 2 compound 3 PA-3 P-14 HOMO (eV) −4.956 −4.808 −4.844 −4.781

That is, it is shown that the compound of the present invention facilitates hole injection compared to the comparative compounds, thereby improving hole mobility, thereby improving the driving voltage, efficiency, and lifespan of the entire element.

In conclusion, even if the core is the same compound, the physical properties of the compound such as hole characteristics, light efficiency characteristics, energy level (LUMO, HOMO level, T1 level), hole injection & mobility characteristics, and electron blocking characteristics vary depending on the bonding position of the substituent, resulting in completely different element results.

[Example 36] Green Organic Light Emitting Diode (Emitting Auxiliary Layer)

2-TNATA was vacuum-deposited to a thickness of 60 nm on the ITO layer (anode) formed on the glass substrate to form a hole injection layer, and then NPB was vacuum-deposited to a thickness of 60 nm on the hole injection layer to form a hole transport layer. Then, after vacuum deposition of the compound P 2-1 of the present invention to a thickness of 20 nm on the hole transport layer to form an emitting auxiliary layer, and on the emitting auxiliary layer, CBP was used as a host material and tris(2-phenylpyridine)-iridium(hereinafter, Ir(ppy)₃) was used as a dopant material, doped at a weight ratio of 95:5, and vacuum deposited to a thickness of 30 nm to form an emitting layer. Subsequently, BAlq was vacuum deposited to a thickness of 10 nm on the emitting layer to form a hole blocking layer, Bis(10-hydroxybenzo[h]quinolinato)beryllium (hereinafter, BeBq₂) was vacuum deposited to a thickness of 40 nm on the hole blocking layer to form an electron transport layer. Thereafter, an electron injection layer was formed by depositing LiF, an alkali metal halide, to a thickness of 0.2 nm, and subsequently, Al was deposited to a thickness of 150 nm to form a cathode, thereby manufacturing an organic light emitting diode.

[Example 37] to [Example 47] Green Organic Light Emitting Diode (Emitting Auxiliary Layer)

An organic light emitting diode was manufactured in the same manner as in Example 36, except that the compound of the present invention described in Table 7 below was used instead of the compound P2-1 as the emitting auxiliary layer material.

[Comparative Example 4] to [Comparative Example 6]

An organic light emitting diode was manufactured in the same manner as in Example 36, except that Comparative Compound 2 and Comparative Compound 4 were used, respectively, instead of the compound P2-1 as the emitting auxiliary layer material.

Electroluminescence (EL) characteristics were measured by PR-650 of photoresearch company by applying a forward bias direct current voltage to the organic light emitting diode prepared according to Examples 36 to 47 and Comparative Example 4 to 6 of the present invention, T95 life was measured through a life measurement equipment manufactured by McScience at a luminance of 5000 cd/m², and the measurement results are shown in Table 7 below.

TABLE 7 Voltage Current Density Brightness Efficiency Lifetime CIE compound (V) (mA/cm²) (cd/m²) (cd/A) T(95) x y comparative comparative 6.5 33.1 5000.0 15.1 80.4 0.32 0.64 example (4) compound 2 comparative comparative 6.3 24.9 5000.0 20.1 88.6 0.30 0.64 example (5) compound 3 comparative comparative 5.9 19.3 5000.0 25.9 105.7 0.32 0.63 example (6) compound 4 example(36) P2-1 5.1 10.6 5000.0 47.2 133.2 0.33 0.60 example(37) P2-3 5.1 10.3 5000.0 48.4 135.1 0.33 0.61 example(38) P2-7 5.3 11.2 5000.0 44.5 128.7 0.34 0.60 example(39) P2-12 5.2 10.7 5000.0 46.7 122.6 0.30 0.62 example(40) P2-14 5.1 11.3 5000.0 44.2 127.1 0.32 0.60 example(41) P2-22 5.1 11.2 5000.0 44.7 122.5 0.30 0.62 example(42) P2-28 5.2 10.8 5000.0 46.4 132.5 0.34 0.65 example(43) P2-37 5.4 12.8 5000.0 39.0 120.2 0.34 0.60 example(44) P2-39 5.3 12.7 5000.0 39.3 131.5 0.32 0.64 example(45) P2-40 5.4 12.9 5000.0 38.8 120.8 0.34 0.61 example(46) P2-46 5.3 11.1 5000.0 45.0 124.2 0.31 0.62 example(47) P2-50 5.2 12.2 5000.0 41.0 126.6 0.31 0.62

As can be seen from the results in Table 7, when a green organic light emitting diode is manufactured using the material for an organic light emitting diode of the present invention as an emitting auxiliary layer material, compared to the comparative compound 4 to 6, and the driving voltage of the organic light emitting diode could be lowered and the efficiency and lifespan were significantly improved.

First, the device result using Comparative Compound 3 with arylamine bonded at the 2 position of the xanthene core was slightly improved than Comparative Compound 2 with arylamine bonded at the 3 position of the xanthene core, and the device result of Comparative Compound 4 in which one more xanthene was bonded as a substituent of the amine group was improved compared to Comparative Examples 4 and 5.

The compound of the present invention is a compound characterized in that an amine group is bonded to 2 position of the xanthene core, and as a substituent of the amine group bonded to the core, one is bonded with 1 position of the dibenzofuran or dibenzothiophene, and the other is bonded with xanthene one more, and it can be seen that the device results of Examples 36 to 47 made of the compounds of the present invention having such characteristics are remarkably excellent.

This is as described in Table 5 above, it is suggested that the compounds of the present invention having a substituent at a specific bonding site may have significantly different chemical and physical properties from those of the Comparative Example compounds, thereby leading to improved device results.

Additionally, referring to Table 8 below, which lists the HOMO values of Comparative Compound 4 and the compound of the present invention, it can be seen that the HOMO value of Compound P 2-3 of the present invention, in which an amine group is bonded to the 2 position of the core, and one more xanthene is bonded at the same time as 1 position of dibenzofuran as a substituent of the bonded amine group, is higher than that of Comparative Compound 4.

TABLE 8 Comparative compound 4 P2-3 HOMO (eV) −4.856 −4.788

That is, it is judged that the compound of the present invention can more efficiently transport holes in the hole transport layer, as a result, it is believed that the charge balance of holes and electrons in the emitting layer is increased, thereby improving the driving voltage, efficiency, and lifespan of the entire device.

In the case of the emitting auxiliary layer, it is necessary to grasp the correlation between the hole transport layer and the emitting layer (host), even if a similar core is used, it will be very difficult for a person skilled in the art to infer the characteristics exhibited in the emitting auxiliary layer in which the compound of the present invention is used.

In addition, the device characteristics in which the compound of the present invention was applied to only one of the emitting auxiliary layers were described in the result of evaluation of manufacture of the element above, but it may be applied to a case where a hole transport layer or both a hole transport layer and an emitting auxiliary layer are formed by using the compound of the present invention.

[Example 48] Green Organic Light Emitting Diode (Emitting Auxiliary Layer)

First, on an ITO layer (anode) formed on a glass substrate, 2-TNATA was vacuum-deposited to a thickness of 60 nm to form a hole injection layer, and NPB as a hole transport compound on the hole injection layer was vacuum-deposited to a thickness of 60 nm to form a hole transport layer. Subsequently, after vacuum deposition of the compound P3-1 of the present invention to a thickness of 20 nm on the hole transport layer to form a first emitting auxiliary layer, a second emitting auxiliary layer was formed by vacuum depositing PA-5 to a thickness of 5 nm on the first emitting auxiliary layer. Then, CBP was used as a host material on the second emitting auxiliary layer, and Ir(ppy)₃ was used as a dopant material and doped at a weight ratio of 95:5 to form an emitting layer by vacuum deposition to a thickness of 30 nm on the emitting auxiliary layer. Next, BAlq was vacuum-deposited to a thickness of 5 nm on the emission layer to form a hole blocking layer, and BeBq₂ was vacuum-deposited to a thickness of 40 nm on the hole blocking layer to form an electron transport layer.

Thereafter, the electron injection layer is formed by depositing LiF, an alkali metal halide, to a thickness of 0.2 nm on the electron transport layer, and then Al is deposited on the electron injection layer to a thickness of 150 nm to form a cathode to form an organic electroluminescent device.

[Example 49] to [Example 58]

An organic electroluminescent device was manufactured in the same manner as in Example 48, except that the compound of the present invention described in Table 9 was used as the material of the first emitting auxiliary layer or the second emitting auxiliary layer.

Example 7

An organic electroluminescent device was manufactured in the same manner as in Example 48, except that Comparative Compound 4 was used as both the first emitting auxiliary layer and the second emitting auxiliary layer material.

Example 8

An organic electroluminescent device was manufactured in the same manner as in Example 48, except that Comparative Compound 4 was used instead of Compound P3-1 of the present invention as the first emitting auxiliary layer material.

Example 9

An organic electroluminescent device was manufactured in the same manner as in Example 48, except that PA-4 was used instead of the compound P3-1 of the present invention as the first emitting auxiliary layer material, and Comparative Compound 4 was used instead of PA-5 as the second emitting auxiliary layer material.

To the OLED prepared according to Examples 48 to 58 and Comparative Examples 7 to 9 of the present invention, a forward bias direct current voltage was applied, and electroluminescent (EL) properties were measured using PR-650 of Photoresearch Co., and T95 life was measured using a life measuring apparatus manufactured by McScience Inc. with a reference luminance of 5000 cd/m². In the following table 9, the manufacture of a device and the results of evaluation are shown.

TABLE 9 1^(st) 2^(nd) emitting emitting Current auxiliary auxiliary Density Brightness Efficiency layer layer Voltage (mA/cm²) (cd/m²) (cd/A) T(95) comparative comparative comparative 6.1 20.7 5000.0 24.2 96.1 example(7) compound 4 compound 4 comparative comparative PA-5 6.2 19.2 5000.0 26.1 108.9 example(8) compound 4 comparative PA-4 comparative 5.7 20.0 5000.0 25.0 98.5 example(9) compound 4 example(48) P3-1 PA-5 5.1 10.9 5000.0 46.0 131.3 example(49) P3-3 PA-5 5.1 10.6 5000.0 47.3 137.0 example(50) P3-16 PA-5 4.8 11.1 5000.0 45.1 141.2 example(51) P3-18 PA-5 4.9 11.6 5000.0 43.1 136.4 example(52) P3-24 PA-5 5.0 11.8 5000.0 42.3 130.6 example(53) PA-4 P3-27 5.2 11.5 5000.0 43.4 135.7 example(54) PA-4 P3-38 5.3 11.2 5000.0 44.6 136.8 example(55) P3-3 P3-3 5.2 12.1 5000.0 41.2 128.8 example(56) P3-16 P3-16 5.1 13.0 5000.0 38.4 134.7 example(57) P3-18 P3-18 5.1 14.0 5000.0 35.6 133.1 example(58) P3-38 P3-38 5.4 12.3 5000.0 40.5 120.4

As can be seen in Table 9, when a green organic light emitting diode is manufactured using the material for an organic electronic element of the present invention as an emitting auxiliary layer material, compared to Comparative Examples 7 to 9 using the comparative compound, the driving voltage of the organic electric element may be lowered, as well as efficiency and lifespan may be improved.

First, compared to Comparative Compound 4, the device results of Examples 48 to 58 using the compound of the present invention were remarkably superior. Comparing Comparative Compound 4 and the compound of the present invention, Comparative Compound 4 and the compound of the present invention have the same point that 2 xanthene cores are bonded to the amine group, but in the compound of the present invention, the amine group is bound only to xanthene, whereas the comparative compound 4 has a structure in which one amine group is bound to xanthene and the other is bound to fluorene.

In this case, the chemical and physical properties may be remarkably different depending on the substituent at the specific bonding site, and thus the device result may be different.

Table 10 below shows the HOMO and T1 values of Comparative Compound 4 and P3-3 and P3-16, compounds of the present invention.

TABLE 10 compound 4 P3-3 P3-16 HOMO (eV) −4.856 −4.742 −4.669 T1 (eV) 2.654 3.001 2.762

As can be seen in Table 10, in the case of the compound of the present invention, it can be seen that HOMO is higher than that of Comparative Compound 4, and T1 is also increased. Accordingly, as the HOMO increases, hole characteristics increase, and hole injection occurs rapidly. As a result, it is determined that the mobility of holes is improved and the driving voltage is decreased. Also, since the high T1 prevents electrons from being injected from the host to the hole transport layer, the overall efficiency and lifespan of the device seems to be improved.

In other words, the compound of the present invention facilitates hole injection compared to Comparative Compound 4, resulting in excellent hole mobility, and due to the high T1, electrons are further blocked, thereby increasing the charge balance of the holes and electrons in the emitting layer, which is believed to improve the performance of the entire device.

In conclusion, even if the core is the same compound, the properties of the compound such as hole characteristics, light efficiency characteristics, energy level (LUMO, HOMO level, T1 level), hole injection & mobility characteristics, and electron blocking characteristics vary depending on the bonding position of the substituent, and this suggests that a completely different device result may be derived.

In the case of an emitting auxiliary layer, it is necessary to grasp the correlation between the hole transport layer and the emitting layer (host), therefore even if a similar core is used, it will be very difficult for a person skilled in the art to infer the characteristics exhibited in the emitting auxiliary layer in which the compound of the present invention is used.

In addition, in the evaluation results of the device fabrication described above, the device characteristics in which the compound of the present invention is applied only to the emitting auxiliary layer have been described, but the compound of the present invention may be applied to the hole transport layer or both the hole transport layer and the emitting auxiliary layer may be used.

Although exemplary embodiments of the present invention have been described for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims. Therefore, the embodiment disclosed in the present invention is intended to illustrate the scope of the technical idea of the present invention, and the scope of the present invention is not limited by the embodiment.

The scope of the present invention shall be construed on the basis of the accompanying claims, and it shall be construed that all of the technical ideas included within the scope equivalent to the claims belong to the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS 100, 200, 300: organic electronic element 110: the first electrode 120: hole injection layer 130: hole transport layer 140: emitting layer 150: electron transport layer 160: electron injection layer 170: second electrode 180: light efficiency enhancing Layer 210: buffer layer 220: emitting-auxiliary layer 320: first hole injection layer 330: first hole transport layer 340: first emitting layer 350: first electron transport 360: first charge generation layer layer 361: second charge generation 420: second hole injection layer layer 430: second hole transport layer 440: second emitting layer 450: second electron transport layer CGL: charge generation layer ST1: first stack ST2: second stack 

What is claimed is:
 1. A compound represented by Formula 7:

wherein: 1) R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷ and R²⁸ are each independently selected from the group consisting of hydrogen; deuterium; halogen; cyano; nitro; a C₆-C₆₀ aryl group; a fluorenyl group; a C₂-C₆₀ heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si or a fused ring group of a C₃-C₆₀ aliphatic ring and a C₆-C₆₀ aromatic ring; a C₁-C₆₀ alkyl group; a C₂-C₆₀ alkenyl group; a C₂-C₆₀ alkynyl group; a C₁-C₆₀ alkoxy group; and a C₆-C₆₀ aryloxy group, and where they are plural, adjacent R²¹s, adjacent R²²s, adjacent R²³s, adjacent R²⁴s, adjacent R²⁵s, adjacent R²⁶s, adjacent R²⁷s, or adjacent R²⁸s are optionally bonded to each other to form a ring, 2) W¹ and W² are each independently O or S, 3) L¹¹ is a single bond; a C₆-C₆₀ arylene group; a fluorenylene group; a C₂-C₆₀ heterocyclic group containing at least one hetero atom of O, N, S, Si and a fused ring group of a C₃-C₆₀ aliphatic ring and a C₆-C₆₀ aromatic ring, 4) Ar¹¹ is a C₆-C₆₀ aryl group, 5) a1, a3, a4, a6, a7 and a8 are each independently an integer of 0 to 4; and a2 and a5 are each independently an integer of 0 to 3, wherein the aryl group, arylene group, heterocyclic group, fluorenyl group, fluorenylene group, aliphatic ring group, fused ring group, alkyl group, alkenyl group, alkynyl group, alkoxyl group and aryloxy group may be substituted with one or more substituents selected from the group consisting of deuterium; halogen; a silane group; a siloxane group; a boron group; a germanium group; a cyano group; a nitro group; a C₁-C₂₀ alkylthio group; a C₁-C₂₀ alkoxy group; a C₁-C₂₀ alkyl group; a C₂-C₂₀ alkenyl group; a C₂-C₂₀ alkynyl group; a C₆-C₂₀ aryl group; a C₆-C₂₀ aryl group substituted with deuterium; a fluorenyl group; a C₂-C₂₀ heterocyclic group; a C₃-C₂₀ cycloalkyl group; a C₇-C₂₀ arylalkyl group and a C₈-C₂₀ arylalkenyl group, wherein the substituents may be bonded to each other to form a saturated or unsaturated ring, wherein the term ‘ring’ means a C₃-C₆₀ aliphatic ring or a C₆-C₆₀ aromatic ring or a C₂-C₆₀ heterocyclic group or a fused ring formed by the combination thereof.
 2. The compound of claim 1, wherein Formula 7 is represented by one of Formulas 7-1 to 7-3:

wherein R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷ and R²⁸, W¹, W², L¹¹, Ar¹¹, and a1, a2, a3, a4, a5, a6, a7 and a8 are the same as defined in claim
 1. 3. The compound of claim 1, wherein L¹¹ is represented by one of Formulas a-1 to a-5:

wherein: 1) R³⁰, R³¹, R³², R³³, R³⁴, R³⁵, R³⁶ and R³⁷ are the same as the definition of R²¹ in claim 1, 2) b1, b3, b4 and b8 are each independently an integer of 0 to 4; b2 is an integer of 0 to 6; b5 and b6 are each independently an integer of 0 to 3; and b7 is an integer of 0 to 2, 3) Z¹ is O or S, 4) * means a position bonded to N (nitrogen) in Formula 7, and *2 means a position bonded to Ar¹¹ in Formula
 7. 4. The compound of claim 1, wherein Formula 7 is represented by Formula 7-4 or Formula 7-5:

wherein: 1) R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷ and R²⁸ are the same as defined in claim 1, 2) R³⁰, R³⁴ and R³⁵ are the same as the definition of R²¹ in claim 1, 3) W¹, W², L¹¹, Ar¹¹, a1, a2, a3, a4, a5, a6, a7 and a8 are the same as defined in claim 1, 4) b1 is an integer of 0 to 4; and b5 and b6 are each independently an integer of 0 to 3, and 5) Z¹ is O or S.
 5. The compound of claim 1, wherein Formula 7 is represented by Formula 7-6:

wherein: 1) R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷ and R²⁸, a1, a2, a3, a4, a5, a6, a7 and a8, W¹ and W² are the same as defined in claim 1, 2) R³⁰ and R⁴⁰ is the same as the definition of R²¹ in claim 1, 3) b1 is an integer of 0 to 4, and 4) c1 is an integer of 0 to
 5. 6. The compound of claim 1, wherein Formula 7 is represented by Formula 7-7:

wherein: 1) R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷ and R²⁸, a1, a2, a3, a4, a5, a6, a7 and a8, W¹ and W² are the same as defined in claim 1, 2) R³⁰ and R⁴⁰ is the same as the definition of R²¹ in claim 1, 3) b1 is an integer of 0 to 4, 4) c1 is an integer of 0 to
 5. 7. The compound of claim 1, selected from the group consisting of compounds P2-46, P2-47, and P3-1 to P3-40:


8. An organic electronic element comprising a first electrode, a second electrode, and an organic material layer formed between the first and the second electrodes, wherein the organic material layer comprises a compound represented by Formula 7 of claim
 1. 9. The organic electronic element of claim 8, wherein the organic material layer comprises at least one of a hole injection layer, a hole transport layer, an emitting auxiliary layer, an emitting layer, an electron transport auxiliary layer, an electron transport layer, and an electron injection layer.
 10. The organic electronic element of claim 8, wherein the organic material layer comprises an emitting auxiliary layer.
 11. The organic electronic element of claim 8, wherein the organic material layer comprises an emitting layer, a hole transport layer formed between the anode and the emitting layer, and a plurality of emitting auxiliary layers formed between the hole transport layer and the emitting layer, and at least one of the plurality of emitting auxiliary layers comprises the compound represented by Formula
 7. 12. The organic electronic element of claim 11, wherein the plurality of emitting auxiliary layers comprises a first emitting auxiliary layer adjacent to the hole transport layer and a second emitting auxiliary layer adjacent to the emitting layer.
 13. The organic electronic element of claim 12, wherein the first emitting auxiliary layer comprises the compound represented by Formula
 7. 14. The organic electronic element of claim 12, wherein the second emitting auxiliary layer comprises the compound represented by Formula
 7. 15. The organic electronic element of claim 8, further comprising a light efficiency enhancing layer formed on at least one surface of the anode and the cathode opposite to the organic material layer.
 16. The organic electronic element of claim 8, wherein the organic material layer comprises at least 2 stacks of layers each including a hole transport layer, an emitting layer, and an electron transport layer sequentially formed on the anode.
 17. The organic electronic element of claim 16, wherein the organic material layer further comprises a charge generation layer formed between the at least 2 stacks of layers.
 18. An electronic device comprising: a display device including the organic electric element of claim 8; and a control unit for driving the display device.
 19. The compound of claim 18, wherein the organic electronic element is at least one of an OLED, an organic solar cell, an organic photo conductor, an organic transistor and an element for monochromic or white illumination. 